JP2009045618A - Catalyst for metathesis reaction - Google Patents

Abstract

A catalyst for a metathesis reaction is provided.
Novel catalysts for metathesis reactions, particularly nitrile rubber metathesis, are provided.
[Selection figure] None

Description

  The present invention relates to transition metal-carbene complex catalysts, processes for their preparation, and their use as catalysis for metathesis reactions, in particular nitrile rubber metathesis.

  Metathesis reactions are widely used in various chemical syntheses, such as ring-closing metathesis (RCM), crossover metathesis (CM), ring-opening metathesis (ROM), ring-opening metathesis polymerization (ROMP), cyclic diene metathesis polymerization (ADMET), self-metathesis, It is used in the form of reaction of alkene and alkyne (enyne reaction), polymerization of alkyne, and olefination of carbonyl ((Patent Document 1) and (Non-Patent Document 1)). Metathesis reactions are employed, for example, for the synthesis of olefins, for the ring-opening polymerization of norbornene derivatives, for the depolymerization of unsaturated polymers, and for the synthesis of telechelic polymers.

  In known metal-carbene complexes, the carbene group has various structures. (Patent Document 2) and (Patent Document 1) disclose, for example, a metathesis catalyst basically having the following structure:

［式中、Ｍがオスミウムまたはルテニウムであり、ＲおよびＲ^１が、広い範囲の構造を有する有機基であり、ＸおよびＸ^１が、アニオン性配位子であり、ＬおよびＬ^１が、電荷を持たない電子供与体である］。文献においては、そのようなメタセシス触媒において慣用される「アニオン性配位子」という用語は、金属中心から個別に見た場合に、閉じた電子殻に対して負に荷電している配位子を指している。

[Wherein M is osmium or ruthenium, R and R ¹ are organic groups having a wide range of structures, X and X ¹ are anionic ligands, and L and L ¹ are charged. It is an electron donor that does not have a]. In the literature, the term "anionic ligand" commonly used in such metathesis catalysts is a ligand that is negatively charged with respect to a closed electron shell when viewed individually from the metal center. Pointing.

  One particular representative of this type of compound is the compound known as "Grubbs (I) catalyst":

  Further, (Patent Document 3) discloses a group of catalysts called “Grubbs (II) catalysts” in the technical field.

  (Patent Document 4) further discloses a metathesis catalyst of the following type, which is also referred to as a “Hoveyda catalyst” in the literature.

  (Patent Document 5) further discloses a metathesis catalyst of the following type, which is also referred to as a “glare catalyst” in the literature.

  Further, Patent Document 6 discloses a hexacoordination complex catalyst, which is known by the name of “Grubbs (III) catalyst”.

  Furthermore, a catalyst in which two substituents located on the carbon atom of the carbene group therein are crosslinked is also known.

  According to Fuersner et al. (Non-Patent Document 2), a first representative of the above-mentioned type of compound was prepared by Hill et al. (Non-Patent Document 3). However, they initially applied the wrong structure to the reaction product. Its correct structure was determined by Huersner et al. (Non-Patent Document 4). This catalyst is the one listed above as the Hill-Hülsner catalyst. A derivative of this catalyst that contains an NHC ligand instead of a phosphine ligand was described in Nolan (Patent Document 7). Those derivatives described by Nolan are also suitable as starting materials for further synthesis of ruthenium-carbene complexes by cross-metathesis (patent document 8).

On page 8, paragraph [0087] of (Patent Document 9), a carbene ligand in which the groups R ¹ and R ² are bridged (the cyclic group obtained thereby may be aliphatic or aromatic) And catalysts containing substituents or heteroatoms are described. This cyclic group is typically described as having 4 to 12, preferably 5 to 8 ring atoms. Clear examples of such cyclic groups are not described and are not self-evident.

  No other catalyst is currently known in which the two substituents located above the carbon atom of the carbene group are bridged.

(Patent Document 1), page 7, lines 39 to 40, Grubbs tried to react RuCl ₂ (= CHR) (PPh ₃ ) ₂ with 9-diazafluorene, but was not successful. is there. He writes, “However, no reaction with diphenyldiazomethane or 9-diazafluorene was observed at RT”.

International Publication No. 97/06185 Pamphlet International Publication No. 96/04289 Pamphlet International Publication No. 00/71554 Pamphlet US Patent Application Publication No. 2002 / 0107138A1 International Publication No. 2004/035596 Pamphlet International Publication No. 03/011455 Pamphlet International Publication No. 00/15339 Pamphlet International Publication No. 2004/112951 Pamphlet US Patent Application Publication No. 2003/0100776 Platinum Metals Rev. 2005, 49 (3), 123-137. Chem. Eur. J. et al. , 2001, 7, no. 22, 4811-4820 K. J. et al. Harlow (KJ Harlow), A.H. F. Hill (AF Hill), J.H. D. E. T.A. Wilton-Ely, J. D. E. T. Wilton-Ely. Chem. Soc. Dalton Trans. 1999, 285-291. J. et al. Org. Chem. 1999, 64, 8275-8280

  Due to the many potential applications, the need for new catalysts for metathesis reactions remains strong.

  In the present invention, surprisingly, a novel transition metal complex catalyst having a fluorenyl ligand and capable of being used as a catalyst for a metathesis reaction is synthesized by applying specific reaction parameters. Has been found to be possible.

The present invention relates to ruthenium- containing the general structural element (I), wherein the carbon atom marked “ ^* ” is bonded to the catalyst skeleton via one or more double bonds, or Providing an osmium-carbene complex catalyst,

および
Ｒ^１〜Ｒ^８は同一であっても異なっていてもよく、それぞれ、水素、ハロゲン、ヒドロキシル、アルデヒド、ケト、チオール、ＣＦ_３、ニトロ、ニトロソ、シアノ、チオシアノ、イソシアナト、カルボジイミド、カルバメート、チオカルバメート、ジチオカルバメート、アミノ、アミド、イミノ、シリル、スルホネート（−ＳＯ_３ ⁻）、−ＯＳＯ_３ ⁻、−ＰＯ_３ ⁻もしくはＯＰＯ_３ ⁻、またはアルキル、シクロアルキル、アルケニル、アルキニル、アリール、カルボキシレート、アルコキシ、アルケニルオキシ、アルキニルオキシ、アリールオキシ、アルコキシカルボニル、アルキルアミノ、アルキルチオ、アリールチオ、アルキルスルホニル、アルキルスルフィニル、ジアルキルアミノ、アルキルシリル、またはアルコキシシリルであるが、ここで、それらの基は、それぞれ場合によっては、１種または複数のアルキル、ハロゲン、アルコキシ、アリールまたはヘテロアリール基によって置換されているか、またはそれに代えて、基Ｒ^１〜Ｒ^８からの２個の直接隣り合った基が、それらが結合されている環の炭素と一緒になって、架橋によって、環式基、好ましくは芳香族系を形成するか、またはそれに代えて、Ｒ^８が、適切であるならば、ルテニウム−またはオスミウム−カルベン錯体触媒の他の配位子に架橋されていてもよく、
ｍが、０または１であり、そして
Ａが、酸素、硫黄、Ｃ（Ｒ^９Ｒ^１０）、Ｎ−Ｒ^１１、−Ｃ（Ｒ^１２）＝Ｃ（Ｒ^１３）−、−Ｃ（Ｒ^１２）（Ｒ^１４）−Ｃ（Ｒ^１３）（Ｒ^１５）−であるが、ここでＲ^９〜Ｒ^１５は同一であっても異なっていてもよく、それぞれ、基Ｒ^１〜Ｒ^８の意味合いの１つを有している。

And R ^{1 to} R ⁸ may be the same or different and are each hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF ₃ , nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thio, respectively. Carbamate, dithiocarbamate, amino, amide, imino, silyl, sulfonate (—SO ₃ ^— ), —OSO ₃ ^— , —PO ₃ ^— or OPO ₃ ^— , or alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, Alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl, alkylsulfinyl, dialkylamino, alkylsilyl, or alkoxy Cisyl, wherein each of these groups is optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups, or alternatively, groups R ¹ -R Or two directly adjacent groups from ⁸ together with the ring carbon to which they are attached form a cyclic group, preferably an aromatic system, by bridge, or alternatively, R ⁸ may be bridged to other ligands of the ruthenium- or osmium-carbene complex catalyst, if appropriate,
m is 0 or 1, and A is oxygen, sulfur, C (R ⁹ R ¹⁰ ), N—R ¹¹ , —C (R ¹² ) = C (R ¹³ ) —, —C (R ¹² ) ^{(R 14) -C (R 13} ) (R 15) - it is a, wherein ^R 9 ^{to R 15} may be the same or different and each, one meaning of radicals ^R 1 to R ⁸ Have one.

  For purposes of this patent application and invention, all of the general or preferred definitions of groups, parameters, or descriptions set forth above or below may be combined with each other in various ways, i.e., the respective ranges. And a preferred range can be further combined.

  As used in the context of this patent application in connection with various types of metathesis catalysts, the term “substituted” refers to the indicated group or hydrogen atom above the atom in each case the indicated group. The valence of the indicated atom must not be excessive, and a stable compound must be obtained with the substitution.

The catalyst of the present invention includes a structural element of the general formula (I), wherein the carbon atom marked with “ ^* ” is bonded to the catalyst skeleton via one or more double bonds. Yes. In the case where carbon atoms marked with “ ^* ” are bonded to the catalyst skeleton via two or more double bonds, these double bonds may be accumulated or conjugated.

  Accordingly, examples of the catalyst of the present invention having the structural element of the general formula (I) include those of the general formulas (IIa) and (IIb).

［式中、
Ｍが、ルテニウムまたはオスミウムであり、
Ｘ^１およびＸ^２は同一であっても異なっていてもよいが、２個の配位子、好ましくはアニオン性配位子であり、
Ｌ^１およびＬ^２が、同一であっても異なっていてもよい配位子、好ましくは電荷を持たない電子供与体であるが、ここでＬ^２が、それに代えて、基Ｒ^８によって架橋されていてもよく、
ｎが、０、１、２または３、好ましくは０、１または２であり、
ｎ’が１または２、好ましくは１であり、そして
Ｒ^１〜Ｒ^８、ｍ、およびＡが、一般式（Ｉ）におけるのと同じ意味合いを有する］

[Where:
M is ruthenium or osmium;
X ¹ and X ² may be the same or different, but are two ligands, preferably an anionic ligand,
L ¹ and L ² are the same or different ligands, preferably an uncharged electron donor, where L ² is instead bridged by the group R ⁸ You may,
n is 0, 1, 2 or 3, preferably 0, 1 or 2;
n ′ is 1 or 2, preferably 1, and R ^{1 to} R ⁸ , m, and A have the same meaning as in general formula (I)]

In the case of the catalyst according to the invention having the general formula (IIa), the structural element of the general formula (I) has one double bond (n = 0) or 2, 3 or They are connected via four integrated double bonds (when n = 1, 2, or 3). In the case of the catalyst according to the invention having the general formula (IIb), the structural element of the general formula (I) is bound via a conjugated double bond to the metal of the complex catalyst. In either case, there is a double bond on the carbon atom marked with “ ^* ” in the direction of the central metal of the complex catalyst.

  Therefore, the catalysts of the above general formulas (IIa) and (IIb) have the following general structural elements (III) to (IX):

１個または複数の二重結合を介して「^＊」を付けた炭素原子を介して、一般式（Ｘａ）または（Ｘｂ）の触媒骨格に結合されている、触媒が包含される。

Included are catalysts that are bonded to the catalyst backbone of general formula (Xa) or (Xb) via a carbon atom marked with “ ^* ” via one or more double bonds.

［式中、Ｘ^１およびＸ^２、Ｌ^１およびＬ^２、ｎ、ｎ’、ならびにＲ^１〜Ｒ^１５は、一般式（ＩＩａ）および（ＩＩｂ）において述べた一般的な意味合いを有している］

[Wherein X ¹ and X ² , L ¹ and L ² , n, n ′, and R ^{1 to} R ¹⁵ have the general meanings described in general formulas (IIa) and (IIb)] ]

  The ruthenium- or osmium-carbene catalysts of the present invention are typically pentacoordinate.

In the structural element of general formula (I):
R ^{1 to} R ⁸ may be the same or different and are each hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF ₃ , nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate , dithiocarbamate, amino, amido, imino, silyl, sulphonate _{^{(-SO 3 -), - OSO}} 3 -, -PO 3 - or OPO ₃ ^-, or alkyl, preferably _C 1 _{-C 20} - alkyl, in particular _{C 1} -C ₆ - alkyl, cycloalkyl, preferably _C 3 _{-C 20} - cycloalkyl, in particular _C 3 -C ₈ - cycloalkyl, alkenyl, preferably _C 2 _{-C 20} - alkenyl, alkynyl, preferably _C 2 -C ₂₀ - alkynyl, aryl, preferably _C 6 _{-C 24} - aryl, in particular phenyl, carboxylate, preferably _C 1 _{-C 20} - carboxylate, alkoxy, preferably _C 1 _{-C 20} - alkoxy, alkenyloxy, preferably _C 2 _{-C 20} - alkenyloxy, alkynyloxy, preferably the _C 2 _{-C 20} - alkynyloxy, aryloxy, preferably _C 6 _{-C 24} - aryloxy, alkoxycarbonyl, preferably _C 2 _{-C 20} - alkoxycarbonyl, alkylamino, preferably _C 1 _{-C 30} - alkyl amino, alkylthio, preferably _C 1 _{-C 30} - alkylthio, arylthio, preferably _C 6 _{-C 24} - arylthio, alkylsulphonyl, preferably _C 1 _{-C 20} - alkylsulfonyl, alkylsulfinyl, preferably _{C 1} -C ₂₀ - alkylsulfinyl, dialkylamino, preferably di _(C 1 _{~C 20} - alkyl) amino, alkyl silyl, preferably _C 1 _{-C 20} - alkyl silyl or alkoxysilyl, preferably _C 1 _{-C 20,} - An alkoxysilyl group, wherein all of these groups may optionally be substituted by one or more alkyl, halogen, alkoxy-, aryl- or heteroaryl groups; Two directly adjacent groups from R ^{1 to} R ⁸ together with the ring carbon to which they are attached may form a cyclic group, preferably an aromatic system, by bridging. , or alternatively, optionally R ⁸ is, ruthenium - or osmium - bridge to other ligands carbene complex catalyst It may have been,
m is 0 or 1, and A is oxygen, sulfur, C (R ⁹ ) (R ¹⁰ ), N—R ¹¹ , —C (R ¹² ) ═C (R ¹³ ) —, or —C ( ^{R 12) (R 14) -C} (R 13) (R 15) - is a, wherein ^R 9 ^{to R 15} may be the same or different and those in each group ^R 1 to R ⁸ Can have the same preferred meaning.

C ₁ -C ₆ - alkyl is, for example, methyl, ethyl, n- propyl, iso - propyl, n- butyl, sec- butyl, tert- butyl, n- pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl , Neopentyl, 1-ethylpropyl, or n-hexyl.

C ₃ -C ₈ - Cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

C ₆ -C ₂₄ -aryl includes aromatic groups having 6 to 24 skeletal carbon atoms. Suitable monocyclic, bicyclic or tricyclic carbocyclic aromatic groups having 6-10 skeletal carbon atoms can include, for example, phenyl, biphenyl, naphthyl, phenanthrenyl, and anthracenyl.

X ¹ and X ²
In general formulas (IIa) and (IIb) and similar to general formulas (Xa) and (Xb), X ¹ and X ² are, for example, hydrogen, halogen, pseudohalogen, linear or branched C ₁ -C ₃₀ - _{alkyl, C} 6 _{~C 24} - _{aryl, C} 1 _{~C 20} - _{alkoxy, C} 6 _{~C 24} - _{aryloxy, C} 3 _{~C 20} - alkyl _{diketonate, C} 6 _{~C 24} - aryldi _{Ketoneto, C} 1 _{~C 20} - _{carboxylate, C} 1 _{~C 20} - alkyl _{sulfonates, C} 6 _{~C 24} - aryl _{sulfonate, C} 1 _{~C 20} - _{alkylthiol, C} 6 _{~C 24} - aryl thiol, _{C 1} -C ₂₀ - alkylsulfonyl or _C 1 _{~C 20,} - may be a alkylsulfinyl group.

The above-mentioned groups X ¹ and X ² are substituted by one or more further groups, for example halogen, preferably fluorine, C ₁ -C ₁₀ -alkyl, C ₁ -C ₁₀ -alkoxy or C ₆ -C ₂₄ -aryl may be, these groups are more halogen, preferably fluorine, C 1 _-C 5 _- by one or more substituents selected from the group consisting of alkoxy and phenyl _- alkyl, C 1 _-C 5 May be substituted.

In preferred embodiments, X ¹ and X ² may be the same or different and each is halogen, in particular fluorine, chlorine, bromine or iodine, benzoate, C ₁ -C ₅ -carboxylate, C ₁ -C ₅ - alkyl, _phenoxy, C 1 -C ₅ - _alkoxy, C 1 -C ₅ - alkyl _thiol, C 6 _{-C 24} - aryl _thiol, C 6 _{-C 24} - aryl or _C 1 -C ₅ - alkyl sulfonates It is.

In particularly preferred embodiments, X ¹ and X ² are the same and are each chlorine, CF ₃ COO, CH ₃ COO, CFH ₂ COO, (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ). _{CO, (CF 3) (CH} 3) 2 CO, PhO ( phenoxy), MeO (methoxy), EtO (ethoxy), tosylate _{(p-CH 3 -C 6 H} 4 -SO 3), mesylate (2,4, it is 6-trimethylphenyl) or _CF 3 SO ₃ (trifluoromethanesulphonate).

Ligands L ¹ and L ²
In the general formulas (IIa) and (IIb) and likewise in the general formulas (Xa) and (Xb), L ¹ and L ² may be the same or different ligands, preferably charged. It is an electron donor that does not have it.

The two ligands L ¹ and L ² are, for example, independently of one another, phosphine, sulfonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, It can be a pyridine, thioether or imidazolidine ("Im") ligand.

Preferably, the two ligands L ¹ and L ² are each independently of each other a phosphine ligand of the formula P (L ³ ) ₃ wherein the group L ³ is the same or different. At best, each represents an alkyl, preferably _C 1 _{-C 10} - alkyl, particularly preferably _C 1 -C ₅ - alkyl, cycloalkyl, preferably _C 3 _{-C 20} - cycloalkyl, particularly preferably _C 3 -C ₈ -Cycloalkyl, very particularly preferably cyclopentyl, cyclohexyl and neopentyl, aryl, preferably C ₆ -C ₂₄ -aryl, particularly preferably phenyl or tolyl), sulfonated phosphine ligands of the formula P (L ⁴ ) ₃ (wherein ^{L 4} represents a mono-sulphonate or Multicontexted sulfonate ligands _{^{L 3), C 6 ~C 24}} - Ali Ruhosufinaito or _C 1 _{-C 10} - alkyl phosphinite _ligand, C 6 _{-C 24} - aryl phosphonite or _C 1 _{-C 10} - alkyl phosphonite _ligand, C 6 _{-C 24} - aryl phosphites or C ₁ -C ₁₀ - alkyl phosphite _{ligand, C} 6 _{~C 24} - aryl arsine or _C 1 _{-C 10} - alkyl arsine _{ligand, C} 6 _{~C 24} - aryl amine or _C 1 _{-C 10} - alkyl amines ligand, a pyridine _ligand, C 6 _{-C 24} - aryl sulfoxide or _C 1 _{-C 10} - alkyl sulphoxide _ligand, C 6 _{-C 24} - aryl ether or _C 1 _{-C 10} - alkyl ether ligand _or, C 6 _{-C 24} - aryl amide or _C 1 _{-C 10} - alkyl Amide ligands, each of which may be mono- or poly-substituted, for example by a phenyl group, where the substituent is further one or more halogen, C ₁ -C ₅ -alkyl or C it may be substituted by ₁ -C ₅ alkoxy group.

The term “phosphine” includes, for example, PPh ₃ , P (p-Tol) ₃ , P (o-Tol) ₃ , PPh (CH ₃ ) ₂ , P (CF ₃ ) ₃ , P (p-FC ₆ H). _{4) 3, P (p-} CF 3 C 6 H 4) 3, P (C 6 H 4 -SO 3 Na) 3, P (CH 2 C 6 H 4 -SO 3 Na) 3, P ( _{isopropyl) 3} , _P (CHCH _{3 (CH} 2 CH ₃₎₎ 3, P _{(cyclopentyl)} 3, include P _(cyclohexyl) 3, P _{(neopentyl) 3,} and P (Neo _{phenyl) 3.}

  The term “phosphinite” includes, for example, triphenylphosphinite, tricyclohexylphosphinite, triisopropylphosphinite, and methyldiphenylphosphinite.

  The term “phosphite” includes, for example, triphenyl phosphite, tricyclohexyl phosphite, tri-tert-butyl phosphite, triisopropyl phosphite, and methyldiphenyl phosphite.

  The term “stibine” includes, for example, triphenylstibine, tricyclohexylstibine, and trimethylstibine.

  The term “sulfonate” includes, for example, trifluoromethanesulfonate, tosylate, and mesylate.

The term “sulfoxide” includes, for example, CH ₃ S (═O) CH ₃ and (C ₆ H ₅ ) ₂ SO.

The term “thioether” includes, for example, CH ₃ SCH ₃ , C ₆ H ₅ SCH ₃ , CH ₃ OCH ₂ CH ₂ SCH ₃ , and tetrahydrothiophene.

  For the purposes of this patent application, the term “pyridine” is used as a generic term including all nitrogen-containing ligands as described by Grubbs in WO 03/011455. Examples include: pyridine, picoline (α-, β-, and γ-picoline), lutidine (2,3-, 2,4-, 2,5-, 2,6-, 3, 4- and 3,5-lutidine), collidine (2,4,6-trimethylpyridine), trifluoromethylpyridine, phenylpyridine, 4- (dimethylamino) pyridine, chloropyridine (2-, 3-, and 4) -Chloropyridine), bromopyridine (2-, 3-, and 4-bromopyridine), nitropyridine (2-, 3-, and 4-nitropyridine), quinoline, pyrimidine, pyrrole, imidazole, and phenylimidazole.

  The imidazolidine group (Im) usually has a structure of the general formula (XIa) or (XIb).

［式中、
Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９は同一であっても異なっていてもよく、それぞれ、水素、直鎖状または分岐状のＣ_１〜Ｃ_３０−アルキル、Ｃ_３〜Ｃ_２０−シクロアルキル、Ｃ_２〜Ｃ_２０−アルケニル、Ｃ_２〜Ｃ_２０−アルキニル、Ｃ_６〜Ｃ_２４−アリール、Ｃ_１〜Ｃ_２０−カルボキシレート、Ｃ_１〜Ｃ_２０−アルコキシ、Ｃ_２〜Ｃ_２０−アルケニルオキシ、Ｃ_２〜Ｃ_２０−アルキニルオキシ、Ｃ_６〜Ｃ_２０−アリールオキシ、Ｃ_２〜Ｃ_２０−アルコキシカルボニル、Ｃ_１〜Ｃ_２０−アルキルチオ、Ｃ_６〜Ｃ_２０−アリールチオ、Ｃ_１〜Ｃ_２０−アルキルスルホニル、Ｃ_１〜Ｃ_２０−アルキルスルホネート、Ｃ_６〜Ｃ_２０−アリールスルホネート、またはＣ_１〜Ｃ_２０−アルキルスルフィニルである］

[Where:
R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ may be the same or different, and each represents hydrogen, linear or branched C ₁ -C ₃₀ -alkyl, C ₃ -C ₂₀ -cycloalkyl. , _C 2 ~C ₂₀ - _{alkenyl, C} 2 _{~C 20} - _{alkynyl, C} 6 _{~C 24} - _{aryl, C} 1 _{~C 20} - _{carboxylate, C} 1 _{~C 20} - _{alkoxy, C} 2 _{~C 20} - alkenyloxy , _C 2 ~C ₂₀ - _{alkynyloxy, C} 6 _{~C 20} - _{aryloxy, C} 2 _{~C 20} - _{alkoxycarbonyl, C} 1 _{~C 20} - _{alkylthio, C} 6 _{~C 20} - _{arylthio, C} 1 _{~C 20} - _{alkylsulfonyl, C} 1 _{~C 20} - alkyl _{sulfonates, C} 6 _{~C 20} - arylsulfonate or _C 1 _{~C 20,} - Arukirusurufu Is nil]

If appropriate, one or more of the radicals R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ are replaced with one or more substituents, preferably linear or branched C ₁ -C ₁₀ -alkyl, It can also be substituted by C ₃ -C ₈ -cycloalkyl, C ₁ -C ₁₀ -alkoxy or C ₆ -C ₂₄ -aryl, wherein the abovementioned substituents are additionally one or more groups, preferably halogen, in particular chlorine or _bromine, C 1 -C ₅ - _alkyl, C 1 -C ₅ - by an alkoxy, and a group selected from the group consisting of phenyl, may be substituted.

  For the sake of simplicity only, the structures of the imidazolidine groups represented as general formulas (XIa) and (XIb) are equivalent to the structures of (XIa ′) and (XIb ′) It should be pointed out that the latter is often found in the literature on this imidazolidine group (Im) and emphasizes the carbene nature of the imidazolidine group. This also applies to the related preferred structures (XIIa) to (XIIf) shown below.

In a preferred embodiment of the catalysts of the general formulas (IIa) and (IIb), R ¹⁶ and R ¹⁷ are each independently of one another hydrogen, C ₆ -C ₂₄ -aryl, particularly preferably phenyl, linear or Branched C ₁ -C ₁₀ -alkyl, particularly preferably propyl or butyl, or together with the carbon atom to which they are attached form a cycloalkyl or aryl group, wherein all the above-mentioned groups are linear or branched _C 1 _{-C 10} - _alkyl, C 1 _{-C 10} - _alkoxy, C 6 _{-C 24} - aryl, and hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine Amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, It may be further substituted with one or more additional groups selected from the group consisting of functional groups selected from the group consisting of carboalkoxy, carbamate, and halogen.

In a particularly preferred embodiment, the catalysts of the general formulas (IIa) and (IIb) have one or two imidazolidine groups (Im) as the ligands L ¹ and L ² , where The radicals R ¹⁸ and R ¹⁹ may be identical or different and are each linear or branched C ₁ -C ₁₀ -alkyl, particularly preferably i-propyl or neopentyl, C ₃ -C ₁₀ - cycloalkyl, preferably _adamantyl, C 6 _{-C 24} - aryl, particularly preferably _phenyl, C 1 _{-C 10} - alkyl sulphonates, particularly preferably _{methanesulphonate,} C 6 _{-C 10} - aryl sulphonates, particularly preferably p -Toluenesulfonate.

The above-mentioned groups as meanings of R ¹⁸ and R ¹⁹ are one selected from the group consisting of linear or branched C ₁ -C ₅ -alkyl, in particular methyl, C ₁ -C ₅ -alkoxy, aryl. Or consisting of hydroxy, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen It may be optionally substituted by a functional group selected from the group.

In particular, the radicals R ¹⁸ and R ¹⁹ may be identical or different and are each i-propyl, neopentyl, adamantyl, mesityl or 2,6-diisopropylphenyl.

  Very particularly preferred imidazolidine groups (Im) have the following structures (XIIa) to (XIIf), where Mes is in each case a 2,4,6-trimethylphenyl group: Alternatively, in all cases it is a 2,6-diisopropylphenyl group.

Similarly, one or both of the general formulas (IIa) and (IIb), and also the ligands L ¹ and L ² in the general formulas (Xa) and (Xb), in which at least one of the alkyl groups is Secondary alkyl groups or cycloalkyl groups, preferably isopropyl, isobutyl, sec-butyl, neopentyl, cyclopentyl or cyclohexyl, which may be the same or different trialkylphosphine ligands. preferable.

In the general formulas (IIa) and (IIb), and likewise in the general formulas (Xa) and (Xb), one or both of the ligands L ¹ and L ² in which at least one of the alkyl groups is a second Particular preference is given to trialkylphosphine ligands which are secondary alkyl groups or cycloalkyl groups, preferably isopropyl, isobutyl, sec-butyl, neopentyl, cyclopentyl or cyclohexyl.

Preferred are catalysts of general formula (IIa) or (IIb) having the following general structural unit (I):
M is ruthenium,
X ¹ and X ² are both halogen,
In the general formula (IIa), n is 0, 1 or 2, or in the general formula (IIb), n ′ is 1.
L ¹ and L ² have the general or preferred meaning in the case of general formulas (IIa) and (IIb),
R ^{1 to} R ⁸ have the general or preferred meaning in the case of general formulas (IIa) and (IIb),
m is either 0 or 1,
And if m = 1,
A is oxygen, _{sulfur, C (C} 1 _{~C 10} - _{alkyl) 2, -C (C 1 ~C} 10 - _{alkyl) 2 -C (C 1 ~C 10} - _{alkyl) 2 -, - C (C} 1 -C ₁₀ - _{alkyl) = C (C 1 ~C 10} - alkyl) -, or _{-N (C} 1 _{~C 10} - alkyl).

Very particular preference is given to catalysts of the formulas (IIa) and (IIb) having the following general structural unit (I):
M is ruthenium,
X ¹ and X ² are both chlorine,
In the general formula (IIa), n is 0, 1 or 2, or in the general formula (IIb), n ′ is 1.
L ¹ is an imidazolidine group having one of formulas (XIIa) to (XIIf);
L ² is a sulfonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine group, an imidazolidine group having one of the formulas (XIIa) to (XIIf); Or phosphine ligands, in particular PPh ₃ , P (p-Tol) ₃ , P (o-Tol) ₃ , PPh (CH ₃ ) ₂ , P (CF ₃ ) ₃ , P (p-FC ₆ H ₄ ) _{3 , P (p-CF 3 C} 6 H 4) 3, P (C 6 H 4 -SO 3 Na) 3, P (CH 2 C 6 H 4 -SO 3 Na) 3, P ( _isopropyl) 3, P ( CHCH ₃ (CH ₂ CH ₃ )) ₃ , P (cyclopentyl) ₃ , P (cyclohexyl) ₃ , P (neopentyl) ₃ , or P (neophenyl) ₃ And
R ^{1 to} R ⁸ have the general or preferred meaning in the case of general formulas (IIa) and (IIb),
m is either 0 or 1,
And if m = 1,
A is oxygen, _{sulfur, C (C} 1 _{~C 10} - _{alkyl) 2, -C (C 1 ~C} 10 - _{alkyl) 2 -C (C 1 ~C 10} - _{alkyl) 2 -, - C (C} 1 -C ₁₀ - _{alkyl) = C (C 1 ~C 10} - alkyl) -, or _{-N (C} 1 _{~C 10} - alkyl).

When the group R ⁸ is bridged to another ligand of the catalyst of the invention, the catalysts of the general formulas (IIa) and (IIb) are, for example, the structures of the general formulas (XIIIa) and (XIIIb) have.

［式中、
Ｙ^１が、酸素、硫黄、Ｎ−Ｒ^２１基、またはＰ−Ｒ^２１であり（Ｒ^２１は以下において定義されるものである）、
Ｒ^２０およびＲ^２１は同一であっても異なっていてもよく、それぞれ、アルキル、シクロアルキル、アルケニル、アルキニル、アリール、アルコキシ、アルケニルオキシ、アルキニルオキシ、アリールオキシ、アルコキシカルボニル、アルキルアミノ、アルキルチオ、アリールチオ、アルキルスルホニル、またはアルキルスルフィニル基であるが、それらはすべて、場合によっては、１種または複数のアルキル、ハロゲン、アルコキシ、アリール、またはヘテロアリール基によって置換されていてもよく、
ｐが、０または１であり、そして
Ｙ^２が、ｐ＝１の場合には、−（ＣＨ_２）_ｒ−（ここで、ｒ＝１、２もしくは３）、−Ｃ（＝Ｏ）−ＣＨ_２−、−Ｃ（＝Ｏ）−、−Ｎ＝ＣＨ−、−Ｎ（Ｈ）−Ｃ（＝Ｏ）−であるか、またはそれらに代えて、全体の構造単位「−Ｙ^１（Ｒ^２０）−（Ｙ^２）_ｐ−」が、（−Ｎ（Ｒ^２０）＝ＣＨ−ＣＨ_２−）、（−Ｎ（Ｒ^２０，Ｒ^２１）＝ＣＨ−ＣＨ_２−）であり、そして
Ｍ、Ｘ^１、Ｘ^２、Ｌ^１、Ｒ^１〜Ｒ^８、Ａ、ｍ、およびｎが、一般式（ＩＩａ）および（ＩＩｂ）の場合におけるのと同じ意味合いを有している］

[Where:
Y ¹ is oxygen, sulfur, N—R ²¹ group, or P—R ²¹ (R ²¹ is as defined below);
R ²⁰ and R ²¹ may be the same or different and are each alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio , Alkylsulfonyl, or alkylsulfinyl groups, all of which are optionally substituted by one or more alkyl, halogen, alkoxy, aryl, or heteroaryl groups,
When p is 0 or 1 and Y ² is p = 1, — (CH ₂ ) _r — (where r = 1, 2 or 3), —C (═O) —CH ₂ —, —C (═O) —, —N═CH—, —N (H) —C (═O) —, or alternatively, the entire structural unit “—Y ¹ (R ²⁰ )-(Y ² ) _p — ”is (—N (R ²⁰ ) ═CH—CH ₂ —), (—N (R ²⁰ , R ²¹ ) ═CH—CH ₂ —), and M, X ¹ , X ² , L ¹ , R ^{1 to} R ⁸ , A, m, and n have the same meaning as in the general formulas (IIa) and (IIb)]

  Examples of catalysts of the present invention can include the following structures:

Preparation of the catalyst of the invention:
The synthesis of such ruthenium- or osmium-carbene complex catalysts can be carried out by reacting a suitable catalyst precursor complex with a suitable diazo compound, but the synthesis is carried out at a specific temperature range. At the same time, the molar ratio of the starting materials is within a specific range.

  Accordingly, the present invention provides a catalyst precursor compound represented by the general formula (XVI):

［式中、Ｒ^１〜Ｒ^８、ｍ、およびＡは、一般式（Ｉ）において述べた一般的な意味合いを有する］
の化合物と反応させることによって、一般式（Ｉ）の構造要素を有するルテニウム−またはオスミウム−カルベン触媒を調製するための方法であって、
その反応を、
（ｉ）温度が、−２０℃〜１００℃の範囲、好ましくは＋１０℃〜＋８０℃の範囲、特に好ましくは＋３０〜＋５０℃の範囲で、
（ｉｉ）触媒前駆体化合物の一般式（ＸＶＩ）の化合物に対するモル比が、１：０．５から１：５まで、好ましくは１：１．５から１：２．５まで、特に好ましくは１：２で、実施することを特徴とする方法を提供する。

[Wherein R ^{1 to} R ⁸ , m, and A have the general meanings described in general formula (I)]
A process for preparing a ruthenium- or osmium-carbene catalyst having a structural element of general formula (I) by reacting with a compound of
The reaction
(I) The temperature is in the range of −20 ° C. to 100 ° C., preferably in the range of + 10 ° C. to + 80 ° C., particularly preferably in the range of +30 to + 50 ° C.,
(Ii) The molar ratio of catalyst precursor compound to compound of general formula (XVI) is from 1: 0.5 to 1: 5, preferably from 1: 1.5 to 1: 2.5, particularly preferably 1. : 2 provides a method characterized in that it is implemented.

The compound of the general formula (XVI) is 9-diazofluorene, or various derivatives thereof according to the meanings of the groups R ^{1 to} R ⁸ and A. In the preparation method of the present invention, various 9-diazofluorene derivatives can be used. In this way, a wide variety of fluorenylidene derivatives can be obtained.

  The catalyst precursor compound is a ruthenium or osmium complex catalyst that does not yet contain a ligand containing the general structural element (I).

  In this reaction, the ligand is detached from the catalyst precursor compound, and a carbene ligand containing a general structural element (I) is incorporated.

  Saturated, unsaturated, and aromatic hydrocarbons, ethers, and halogenated solvents are preferred for the reaction to proceed. Chlorinated solvents such as dichloromethane, 1,2-dichloroethane, or chlorobenzene are preferred.

  Usually, the catalyst precursor compound is first charged in the form of a ruthenium or osmium precursor, preferably in a dried solvent. The concentration of ruthenium or osmium precursor in the solvent is usually in the range of 15-25% by weight, preferably in the range of 15-20% by weight. The solution may then be heated. It has been found particularly useful to heat the solution to a temperature in the range of 30-50 ° C. The compound of general formula (XVI), usually dried, preferably dissolved in an anhydrous solvent, is then added. The concentration of the compound of general formula (XVI) in the solvent is preferably in the range of 5 to 15% by weight, preferably about 10% by weight. To complete the reaction, the mixture is allowed to react for an additional 0.5 to 1.5 hours, while maintaining the temperature in the same range as described above, i.e., 30-50 ° C. The solvent is then removed and the residue is purified using, for example, a mixture of hexane and aromatic solvent.

  The catalyst of the present invention is usually not obtained in pure form due to the stoichiometry of the reaction, and the reaction of the compound of general formula (XVI) with the leaving ligand of the catalyst precursor compound used in the reaction Obtained as an equimolar mixture with the product. The leaving ligand is preferably a phosphine ligand. In order to obtain the pure catalyst of the present invention, it is possible to remove the reaction product. However, it is not essential to use the pure catalyst of the present invention in order to initiate the catalytic reaction of the metathesis reaction, and instead use a mixture of this catalyst according to the present invention containing the reaction products described above. It is also possible to do.

  The above method will be described below.

  In the case of catalysts of general formula (IIa) and (IIb), the general formula (XVII):

［式中、
Ｍ、Ｘ^１、Ｘ^２、Ｌ^１およびＬ^２は、一般式（ＩＩａ）および（ＩＩｂ）の場合と同じ一般的な意味合いおよび好ましい意味合いを有し、そして
ＡｂＬが、「脱離配位子」であって、一般式（ＩＩａ）および（ＩＩｂ）におけるＬ^１およびＬ^２と同じ意味合いを有することができるが、好ましくは一般式（ＩＩａ）および（ＩＩｂ）において述べた一般的な意味合いを有するホスフィン配位子である］
の触媒前駆体化合物を、一般式（ＸＶＩ）の化合物と、−２０℃〜１００℃の範囲、好ましくは＋１０℃〜＋８０℃の範囲、特に好ましくは＋３０〜＋５０℃の範囲の温度と、１：０．５から１：５まで、好ましくは１：１．５から１：２．５まで、特に好ましくは１：２の、一般式（ＸＶＩＩ）の触媒前駆体化合物の、一般式（ＸＶＩ）の化合物に対するモル比で、反応させる。

[Where:
M, X ¹ , X ² , L ¹ and L ² have the same general and preferred meanings as in general formulas (IIa) and (IIb), and AbL is a “leaving ligand” A phosphine having the same meaning as L ¹ and L ² in general formulas (IIa) and (IIb), but preferably having the general meanings mentioned in general formulas (IIa) and (IIb) Is a ligand]
A catalyst precursor compound of general formula (XVI) with a temperature in the range of −20 ° C. to 100 ° C., preferably in the range of + 10 ° C. to + 80 ° C., particularly preferably in the range of +30 to + 50 ° C., and 1: 0.5 to 1: 5, preferably 1: 1.5 to 1: 2.5, particularly preferably 1: 2, of the catalyst precursor compound of the general formula (XVII) of the general formula (XVI) The reaction is carried out at a molar ratio to the compound.

  A method for preparing the catalyst belonging to the general formula (II) will be described below with examples. The reaction provides the desired fluorenylidene carbene complex catalyst in a mixture with fluorenylidene triphenylphosphazine.

The catalyst of the present invention, RuCl ₂ (fluorenylidene) (PPh ₃ ) ₂ , shown in the previous scheme, is known from the prior art in that it is significantly more stable than RuCl ₂ (benzylidene) (PPh ₃ ) ₂ . A distinction is made from things. RuCl ₂ (benzylidene) (PPh ₃ ) ₂ is stable in the solid phase, but decomposes in solution even at −60 ° C. (J. Am. Chem. Soc., 1996, 118, 100). In order to improve the stability in solution, RuCl ₂ (benzylidene) (PPh ₃ ) ₂ must be reacted with PCy ₃ to form RuCl ₂ (benzylidene) (PCy ₃ ) ₂ . In the case of the corresponding RuCl ₂ (fluorenylidene) (PPh ₃ ) ₂ , this need not be done. This is economically advantageous.

  The following procedure is useful for introducing one or two Im ligands (formulas (XIa) and (XIb) and further “Im” as defined above for (XIIIa-f)) It turned out to be.

In the first step, the above-described method for preparing the catalyst according to the invention is carried out, wherein all of the ligands L ¹ and L ² , apart from the Im ligand, have the general formula It has the general implications described in (IIa) and (IIb). In the second step, one or both of the ligands L ¹ and L ² in this catalyst according to the invention which already contains the general structural element (I) is replaced by an Im ligand.

This procedure is particularly preferred for preparing the catalyst according to the invention of the formula RuCl ₂ (“fluorenylidene”) (PPh ₃ ) (Im), where “fluorenylidene” is a common structural element ( Although used as a representative of the ligand containing I): preparation first, RuCl ₂ by ligand exchange method _{(PPh 3) 3} from RuCl ₂ ( "fluorenylidene") and _{(PPh 3) 2} In the second step, one of the two triphenylphosphine ligands is replaced by a saturated or unsaturated Im ligand.

  In order to introduce one or more Im ligands, a free carbene such as obtained by the method of Arduengo (J. Am. Chem. Soc., 1995, 117, 11027) is used. It is possible. Alternatively, strong acids such as hydrochloric acid or salts of tetrafluoroboric acid and carbene, or carbene adducts with chloroform, t-butanol, chloral, etc. are used as starting materials. It is described in US Pat. No. 6,613,910 that when a carbene salt or carbene adduct is used, a “free” carbene is generated in situ by a strong base.

  However, by Arduengo, J. et al. Am. Chem. Soc. The free carbene is preferably prepared and isolated by the method described in US Pat. This method, described by Arduengo, has the advantage that both saturated and unsaturated carbenes can be obtained with this method, since US Pat. No. 6,613 , 910, because carbene adducts of unsaturated carbenes cannot be obtained: "Only 4,5-dihydroimidazolium salts form imidazolidene--aromatic imidazolium salts (ie their It is noteworthy that (unsaturated analogues) do not form their adducts under any conditions "(column 19, line 65 to column 20, line 1).

The second step, in which the Im ligand is introduced, is described in the following two-step process by way of example:
The preparation of compounds of general formula (IIa) in which L ¹ and / or L ² is an Im ligand is a general formula (IIa ′):

［式中、Ｘ^１、Ｘ^２、Ｌ^２、ｎ、ｍ、Ａ、およびＲ^１〜Ｒ^８は、一般式（ＩＩａ）におけるのと同じ意味合いを有し、
Ｌ^１およびＬ^２は同一であっても異なっていてもよいが、それぞれ、ホスフィン配位子、好ましくはＰＰｈ_３、Ｐ（ｐ−Ｔｏｌ）_３、Ｐ（ｏ−Ｔｏｌ）_３、ＰＰｈ（ＣＨ_３）_２、Ｐ（ＣＦ_３）_３、Ｐ（ｐ−ＦＣ_６Ｈ_４）_３、Ｐ（ｐ−ＣＦ_３Ｃ_６Ｈ_４）_３、Ｐ（Ｃ_６Ｈ_４−ＳＯ_３Ｎａ）_３、Ｐ（ＣＨ_２Ｃ_６Ｈ_４−ＳＯ_３Ｎａ）_３、Ｐ（イソプロピル）_３、Ｐ（ＣＨＣＨ_３（ＣＨ_２ＣＨ_３））_３、Ｐ（シクロペンチル）_３、Ｐ（シクロヘキシル）_３、Ｐ（ネオペンチル）_３、またはＰ（ネオフェニル）_３である］
の化合物を、一般式（ＸＶＩＩＩａ）または（ＸＶＩＩＩｂ）：

[Wherein X ¹ , X ² , L ² , n, m, A, and R ^{1 to} R ⁸ have the same meaning as in general formula (IIa);
L ¹ and L ² may be the same or different, but are each a phosphine ligand, preferably PPh ₃ , P (p-Tol) ₃ , P (o-Tol) ₃ , PPh (CH ₃ ) ₂ , P (CF ₃ ) ₃ , P (p-FC ₆ H ₄ ) ₃ , P (p-CF ₃ C ₆ H ₄ ) ₃ , P (C ₆ H ₄ —SO ₃ Na) ₃ , P (CH _{2 C 6 H 4 -SO 3 Na} ) 3, P ( _{isopropyl) 3, P (CHCH 3 (} CH 2 CH 3)) 3, P ( _cyclopentyl) 3, P _(cyclohexyl) 3, P _{(neopentyl) 3} or, P (neophenyl) ₃ ]
A compound of the general formula (XVIIIa) or (XVIIIb):

［式中、Ｒ^１６〜Ｒ^１９は、一般式（ＸＩａ）および（ＸＩｂ）において述べた一般的な意味合いを有する］
の化合物と反応させる。

[Wherein R ^{16 to} R ¹⁹ have the general meanings described in the general formulas (XIa) and (XIb)]
Reaction with the compound

In this reaction, ligand L ¹ and / or ligand L ² in formula (IIa ′) is replaced by a ligand of formula (XVIIIa) or (XVIIIb).

This reaction is shown below for a particularly preferred example in which the P (Ph) ₃ ligand is replaced by an Im ligand.

  This reaction is usually carried out at a temperature in the range of -20 ° C to 80 ° C, preferably in the range of 0 ° C to 50 ° C.

When the molar ratio of the compound of general formula (IIa ′) to the compound of formula (XVIIIa) or (XVIIIb) is in the range of 1: 0.5 to 1: 1.5, preferably 1: 1, usually 1 Ligands, L ¹ or L ² are replaced by Im ligands.

  When the molar ratio of the compound of general formula (IIa ′) to the compound of formula (XVIIIa) or (XVIIIb) is from 1: 2 to 1: 5, preferably from 1: 2 to 1: 3, Usually two Im ligands are introduced.

  The reaction is carried out in saturated, unsaturated or aromatic hydrocarbons or in ethers or mixtures thereof. Ethers, particularly diethyl ether, are preferred because the reaction product does not dissolve therein.

Starting from the catalysts of the general formulas (IIa) and (IIb) according to the invention obtained by a two-stage process and still containing the phosphine ligand (L ² ) in addition to the Im ligand (L ¹ ) The phosphine ligand (L ² ), other nitrogen-containing, preferably aromatic heterocycles, in particular pyridine or derivatives thereof, having the implications indicated on pages 10 and 11 of the third step. It can be replaced by a ligand L ^2.

  In these reactions, only nitrogen-containing, preferably aromatic heterocycles are always introduced into the catalyst according to the invention of the general formula (IIa) or (IIb) already containing the structural element (I). .

  The phosphine / pyridine exchange reaction described above is carried out in a manner analogous to that described by Grubbs in WO 03/011455.

  Furthermore, many methods are known from the literature for synthesizing a transition metal complex catalyst having a carbene ligand and basically introducing a carbene ligand into the transition metal complex catalyst. Examples of such documents include International Publication No. 96/04289, International Publication No. 97/06185, International Publication No. 00/71554, US Patent Application Publication No. 2002 / 0107138A1, International Publication. No. 2004/035596 pamphlet, International Publication No. 03/011455 pamphlet and the like. Such synthesis is also known from US 2003/0100776, WO 2003/011455, and WO 2003/087167. One skilled in the art will be able to synthesize the catalysts of the present invention based on such literature methods.

Use of the catalyst of the invention for metathesis:
The present invention further provides the use of the catalyst of the present invention in a metathesis reaction.

  This metathesis reaction is described in WO 97/06185 pamphlet and Platinum Metals Rev. 2005, 49, (3), 123-137, in particular ring-closing metathesis (RCM), cross-metathesis (CM), ring-opening metathesis (ROM), ring-opening metathesis polymerization (ROMP), cyclic Diene metathesis polymerization (ADMET), self-metathesis, reaction of alkene with alkyne (enyne reaction), polymerization of alkyne, and olefination of carbonyl.

  The catalyst of the present invention is suitable for, for example, ring-closing metathesis of diethyl diallylmalonate and diallylmalononitrile under an inert gas atmosphere or aerobic conditions.

  The catalyst system of the present invention is preferably used for the metathesis of nitrile rubber. They are a method for reducing the molecular weight of a nitrile rubber by contacting the nitrile rubber with a catalyst according to the present invention. This reaction is cross-metathesis.

  All of the above-mentioned type (B) catalysts can be used as such in the NBR metathesis reaction mixture or they can be applied and immobilized on a solid support. Suitable solid phases or supports are substances which are first inert to the metathesis reaction mixture and secondly do not adversely affect the activity of the catalyst. Catalyst immobilization can be achieved using, for example, metals, glasses, polymers, ceramics, organic polymer spheres or inorganic sol-gels, carbon black, silica, silicates, calcium carbonate, and barium sulfate. it can.

  The amount of metathesis catalyst per amount of nitrile rubber used depends on the nature and catalytic activity of the particular catalyst. The amount of catalyst used is usually 1 to 1000 ppm, preferably 2 to 500 ppm, in particular 5 to 250 ppm of noble metal, based on the nitrile rubber used.

NBR metathesis can be carried out in the absence or presence of co-olefins. Its co-olefin is preferably a straight-chain or branched C ₂ -C 16 _- olefin. Suitable coolefins are, for example, ethylene, propylene, isobutene, styrene, 1-hexene or 1-octene. It is preferred to use 1-hexene or 1-octene. When the co-olefin is liquid (for example, in the case of 1-hexene), the amount of the co-olefin is preferably in the range of 0.2 to 20% by weight based on the nitrile rubber used. When the co-olefin is gaseous, for example ethylene, the amount of co-olefin is selected and the pressure in the reactor at room temperature is in the range of 1 × 10 ⁵ Pa to 1 × 10 ⁷ Pa, preferably 5 It is preferable to obtain a pressure in the range of 2 × 10 ⁵ Pa to 4 × 10 ⁶ Pa.

  The metathesis reaction can be carried out in a suitable solvent without deactivating the catalyst used or even otherwise adversely affecting the reaction. Suitable solvents include, but are not limited to, dichloromethane, benzene, toluene, methyl ethyl ketone, acetone, tetrahydrofuran, tetrahydropyran, dioxane, and cyclohexane. A particularly preferred solvent is chlorobenzene. In some cases, the co-olefin itself can function as a solvent, for example in the case of 1-hexene, it can be dispensed with without additional additional solvent.

  The concentration of the nitrile rubber used in the metathesis reaction mixture is not strictly limited, but it should be understood that the reaction mixture has an excessively high viscosity, which causes mixing problems and adversely affects the reaction. It is necessary to ensure that there is no. The concentration of NBR in the reaction mixture is preferably in the range from 1 to 25% by weight, particularly preferably in the range from 5 to 20% by weight, based on the total reaction mixture.

  The metathesis decomposition is usually carried out at a temperature in the range of 10 ° C to 150 ° C, preferably in the range of 20 to 100 ° C.

  The reaction time depends on several factors, such as NBR type, catalyst type, catalyst concentration used, reaction temperature, and the like. Under normal conditions, the reaction is typically complete within 3 hours. The progress of the metathesis reaction can be monitored by standard analytical methods such as GPC measurement or viscosity measurement.

  Nitrile rubber (“NBR”) includes a repeat of at least one conjugated diene, at least one α, β-unsaturated nitrile, and, if appropriate, one or more additional copolymerizable monomers in the metathesis reaction. Copolymers or terpolymers having units can be used.

The conjugated diene may be of various types. Preference is given to using (C ₄ -C ₆ ) -conjugated dienes. 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene, or mixtures thereof are particularly preferred. 1,3-butadiene and isoprene or mixtures thereof are particularly preferred. 1,3-butadiene is very particularly preferred.

As the α, β-unsaturated nitrile, various known α, β-unsaturated nitriles can be used, but (C ₃ -C ₅ ) -α, β-unsaturated nitriles such as acrylonitrile, methacrylo Nitrile, ethacrylonitrile or mixtures thereof are preferred. Particularly preferred is acrylonitrile.

  Therefore, a particularly preferred nitrile rubber is a copolymer of acrylonitrile and 1,3-butadiene.

  In addition to the conjugated diene and the α, β-unsaturated nitrile, one or more further copolymerizable monomers known to those skilled in the art, for example α, β-unsaturated monocarboxylic or dicarboxylic acids, their esters or amides Can also be used. As the α, β-unsaturated monocarboxylic acid or dicarboxylic acid, fumaric acid, maleic acid, acrylic acid, and methacrylic acid are preferable. As esters of α, β-unsaturated carboxylic acids, alkyl esters and alkoxyalkyl esters thereof are preferable. Particularly preferred alkyl esters of α, β-unsaturated carboxylic acids are methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and octyl acrylate. Particularly preferred alkoxyalkyl esters of α, β-unsaturated carboxylic acids are methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and methoxyethyl (meth) acrylate. It is also possible to use mixtures of alkyl esters such as those listed above with alkoxyalkyl esters such as those listed above.

  The ratio of conjugated diene to α, β-unsaturated nitrile in the NBR polymer used can be varied within a wide range. The ratio of the conjugated diene or the sum of the conjugated dienes is usually in the range of 40 to 90% by weight, preferably in the range of 60 to 85% by weight, based on the total polymer. The ratio of α, β-unsaturated nitrile or the sum of α, β-unsaturated nitriles is usually 10 to 60% by weight, preferably 15 to 40% by weight, based on the total polymer. In each case, the monomer ratio is 100% by weight in total. The additional monomer can be present in an amount of 0 to 40% by weight, preferably 0.1 to 40% by weight, particularly preferably 1 to 30% by weight, based on the total polymer. In this case, the relevant proportions of conjugated diene or diene and / or α, β-unsaturated nitrile or nitrile are replaced by the proportion of additional monomers, but in each case the proportion of all monomers is summed to 100 weight %.

  The preparation of nitrile rubber by polymerizing the above monomers is well known to those skilled in the art and is comprehensively described in the literature.

  Nitrile rubbers that can be used for the purposes of the present invention are, for example, from the Perbunan® and Krynac® product series from Lanxess Deutschland GmbH. It can also be easily obtained as a product.

The nitrile rubber used for metathesis has a Mooney viscosity (ML1 + 4, 100 ° C.) in the range of 30 to 70, preferably 30 to 50. This is 150 000-500 000, preferably in the range corresponds to a weight average molecular weight _{M w} in the range of 180 000 to 400 000. Furthermore, the nitrile rubber used is a polydisperse PDI = M _w / M _n (where M _w is a weight average) in the range of 2.0 to 6.0, preferably in the range of 2.0 to 4.0. Molecular weight, M _n is the number average molecular weight).

  The Mooney viscosity is measured according to ASTM standard D1646.

The nitrile rubber obtained by the metathesis method of the present invention has a Mooney viscosity (ML1 + 4, 100 ° C.) in the range of 5-30, preferably in the range of 5-20. This is 10 000-100 000, preferably in the range corresponds to a weight average molecular weight _{M w} in the range of 10 000 to 80 000. Furthermore, the obtained nitrile rubber has a polydispersity PDI = M _w / M _{n in} the range of 1.4 to 4.0, preferably in the range of 1.5 to 3.0, where M _n is the number average molecular weight. Is).

Addition of salt in metathesis:
In one embodiment, NBR metathesis can be performed in the presence of one or more salts having the general formula (XIX).
^{Kn + Az-} (XIX)
[Where:
K is a cation and A is an anion and n is 1, 2 or 3 and z is 1, 2 or 3]

  Suitable cations are based on elements from the periodic table (main group and transition group elements) capable of forming cations carrying one, two or three positive charges. It is a thing.

  Suitable cations are, for example, lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, aluminum, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth, scandium. Yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, silver, gold, zinc , Cadmium, mercury, and all elements of the genus of rare earths, in particular cerium, praseodymium and neodymium, and also the actinide elements.

  Further suitable cations are complex cations based on nitrogen, phosphorus and sulfur. For example, use tetraalkylammonium, tetraarylammonium, hydroxylammonium, tetraalkylphosphonium, tetraarylphosphonium, sulfonium, anilinium, pyridinium, imidazolonium, guanidinium, and hydrazinium cations, and even cationic ethylenediamine derivatives Is possible.

In any of the above complex cations, the alkyl group may be the same or different, and each is usually a linear or branched C ₁ -C ₃₀ -alkyl group, preferably C ₁ -C _{20, respectively.} - alkyl group, particularly preferably _C 1 _{-C 18} - alkyl group. These alkyl groups may be further substituted with an aryl group. C ₁ -C ₁₈ -alkyl includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3 -Methylbutyl, neopentyl, 1-ethylpropyl, cyclohexyl, cyclopentyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3 -Methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl , N-tetradecyl, n-hexadecyl, n-octadecyl, and benzyl.

The aryl group in any of the above-described complex cation may be the same or different and each is usually, C 5 _-C 24 _- aryl group, preferably a C ₆ -C 14 _- aryl radical, particularly preferably C ₆ -C ₁₀ - aryl group. Examples of C ₅ -C ₂₄ -aryl are phenyl, o-, p-, m-tolyl, naphthyl, phenanthrenyl, anthracenyl, and fluorenyl.

The [R ³ S] ⁺ type of sulfonium cation has three groups which may be the same or different, and may be aliphatic or aromatic in nature. These groups may be alkyl or aryl groups having the same general meaning, preferred meaning and particularly preferred meaning as described above.

  Particularly suitable complex cations include: benzyldodecyldimethylammonium, didecyldimethylammonium, dimethylanilinium, N-alkyl-N, N-bis (2-hydroxyalkyl) -N-benzylammonium, N , N, N-triethylbenzenemethananium, O-methyluronium, S-methylthiouronium, pyridinium, tetrabutylammonium, tetramethyluronium, tetraacetylammonium, tetrabutylphosphonium, tetraphenylphosphonium, diphenylguanidi Ni, di-o-tolyl-guanidinium, butyldiphenylsulfonium, tributylsulfonium.

  In general formula (I), A is a monovalent, divalent or trivalent charged anion, preferably a halide, pseudohalide, complex anion, anion of organic acid, aliphatic or aromatic sulfonate, aliphatic or Anions from the group consisting of aromatic sulfates, phosphonates, phosphates, thiophosphates, xanthogenates, dithiocarbamates, and non-coordinating anions.

  Suitable halides are fluoride, chloride, bromide, and iodide.

  Suitable pseudohalides are, for example, triiodide, azide, cyanide, thiocyanide, thiocyanate, and interhalide.

  Suitable complex anions include, for example, sulfite, sulfate, dithionite, thiosulfate, carbonate, hydrogen carbonate, perthiocarbonate, nitrite, nitrate, perchlorate, tetrafluoroborate, tetrafluoroaluminate, hexafluorophosphate, Hexafluoroarsenate, hexafluoroantimonate, and hexachloroantimonate.

  Suitable monovalent, divalent, or trivalent charged organic acid anions are monovalent, divalent, or trivalent charged anions of organic carboxylic acids having from 1 to 20 carbon atoms. These organic carboxylic acids may be saturated, monounsaturated or polyunsaturated. Suitable examples are formate, acetate, propionate, butyrate, oleate, palmitate, stearate, versatate, acrylate, methacrylate, crotonate, benzoate, naphthalene carbonate, oxalate, salicylate, terephthalate, fumarate, maleate, itaconate, and abiate.

  Suitable aliphatic or aromatic sulfonates are anthraquinone-2-sulfonate, benzenesulfonate, benzene-1,3-disulfonate, decane-1-sulfonate, hexadecane-1-sulfonate, hydroquinone monosulfonate, methyl-4-toluenesulfonate. , Naphthalene-1-sulfonate, naphthalene-1,5-disulfonate, tosylate, and mesylate.

  Suitable aliphatic or aromatic sulfates are, for example, dodecyl sulfate and alkylbenzene sulfate.

  Suitable phosphonates, phosphates, and thiophosphates are vinyl phosphonate, ethyl phosphonate, butyl phosphonate, cetyl phosphonate, dibutyl phosphate, dioctyl phosphate, dibutyl dithiophosphate, and dioctyl thiophosphate.

  Suitable aliphatic or aromatic xanthogenates are ethyl xanthogenate, butyl xanthogenate, phenyl xanthogenate, benzyl xanthogenate, and the like.

  Suitable aliphatic or aromatic dithiocarbamates are dimethyldithiocarbamate, diethyldithiocarbamate, dibutyldithiocarbamate, and dibenzyldithiocarbamate.

  Non-coordinating anions include, for example, tetrakis [pentafluorophenyl] borate, pentakis [pentafluorophenyl] phosphate, tetrakis [3,5-trifluoromethylphenyl] borate, pentakis [3,5-trifluoromethylphenyl] phosphate, And pentakis [pentafluorophenyl] cyclohexadienyl anion.

  For example, it is preferred to use alkali metal halides such as lithium chloride, lithium bromide, or lithium iodide, and cesium bromide.

  For example, it is preferred to use alkaline earth metal chlorides such as calcium chloride and magnesium chloride.

Amount of salt to nitrile rubber:
In the catalyst system of the present invention, the metathesis catalyst and one or more salts of the general formula (I) are used in a weight ratio of salt: metathesis catalyst of 0.01: 1 to 10,000: 1, preferably 0.00. It is used at 1: 1 to 1000: 1, particularly preferably 0.5: 1 to 500: 1.

  The salt or salts can be added to the metathesis catalyst or solution thereof in or without a solvent.

  Various known solvents can be used as the solvent or dispersion medium used when adding one or more salts to the catalyst or a solution thereof. In order for the salt to be added effectively, the solubility of the salt or salts in the solvent must never be high. Suitable solvents include, but are not limited to, acetone, benzene, chlorobenzene, chloroform, cyclohexane, dichloromethane, dioxane, dimethylformamide, dimethylacetamide, dimethyl sulfone, dimethyl sulfoxide, methyl ethyl ketone, tetrahydrofuran, tetrahydropyran, and toluene. It is not done. It is preferred that the solvent is inert to the metathesis catalyst.

  When the catalyst of the present invention is used for nitrile rubber metathesis, the amount of salt used per amount of rubber to be decomposed is 0.0001 phr to 50 phr, preferably 0.001 phr to 35 phr (phr = rubber) Parts by weight per 100 parts by weight).

  When used for NBR metathesis, the salt can also be added to the solution of the metathesis catalyst in a solvent or dispersion medium or otherwise without a solvent or dispersion medium. As an alternative, it is also possible to add the salt directly to the solution of the nitrile rubber to be decomposed and then add it to the metathesis catalyst.

Addition of transition metal alkoxide:
Transition metal alkoxides can also be added during the metathesis process, particularly the decomposition of metathesis NBR.

They are compounds of general formula (XX):
M ′ (OZ ′) _{m ′} (XX)
[Where:
M ′ is a transition metal of transition group 4, 5 or 6 of the periodic table of elements,
m ′ is 4, 5 or 6 and the radicals Z ′ may be the same or different but each have 1 to 32 carbon atoms and a further 1 to 15 heteroatoms Which may have a linear, branched, aliphatic, cyclic, heterocyclic or aromatic group]

  Suitable transition group 4, 5 or 6 transition metals in the compounds of general formula (XX) are titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten.

  In the compounds of the general formula (XX), the groups Z ′ may be the same or different and have 1 to 30 carbon atoms, further 1 to 15 heteroatoms, preferably nitrogen or oxygen. A linear, branched, aliphatic, cyclic, heterocyclic or aromatic group which may be present.

If the group Z ′ has 1 to 32 carbon atoms and may further have 1 to 15 heteroatoms, preferably nitrogen or oxygen, then Z ′ is linear or branched. C ₁ -C ₃₀ - alkyl, preferably _C 1 _{-C 20} - alkyl, particularly preferably _C 1 _{-C 12} - _alkyl, C 3 _{-C 20} - cycloalkyl, preferably _C 3 _{-C 10} - cycloalkyl, in particular preferably _C 5 -C ₈ - _cycloalkyl, C 2 _{-C 20} - alkenyl, preferably _C 2 _{-C 18} - _alkenyl, C 2 _{-C 20} - alkynyl, formula (-CHZ '' - CHZ '' - A ² _-) in p _-CH 2 -CH ₃ group [wherein, p is an integer of 1 to 10, group Z '' is may be the same or different and each is hydrogen or methyl Located above an adjacent carbon atom Is preferably based on ^{Z 1} are different, and ^{A 2} is oxygen, sulfur or _{-NH, C} 6 ~C ₂₄ - aryl group, preferably a _C 6 _{-C 14} - aryl group or at least one heteroatom, , preferably _C 4 _{-C 23} having a nitrogen or oxygen - is a heteroaryl group.

Preference is given to using compounds of the general formula (XX) as follows:
M ′ is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten;
m ′ is 4, 5 or 6, and Z ′ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl, i-pentyl, t -Pentyl, dodecyl, oleyl, phenyl, or sterically hindered phenyl.

  The compounds of the general formula (I) which are particularly preferably used in the process according to the invention are tetraethoxytitanate, tetraisopropyloxytitanate, tetra-tert-butyloxytitanate, tetra-tert-butyloxyzirconate, pentaethoxyniobate, And pentaethoxy tantalite.

Hydrogenation After metathesis cracking in the presence of the catalyst system of the present invention, the cracked nitrile rubber so obtained can be hydrogenated. This can be done by methods known to those skilled in the art.

  Hydrogenation can be carried out using a homogeneous or heterogeneous hydrogenation catalyst. It is also possible to carry out the hydrogenation in situ, ie in the same reaction vessel in which the metathesis cracking was carried out before, without having to isolate the cracked nitrile rubber. The hydrogenation catalyst is simply introduced into the reaction vessel.

  The catalysts used are usually based on rhodium, ruthenium or titanium, but platinum, iridium, palladium, rhenium, ruthenium, osmium, cobalt or copper are used as metals, or preferably in the form of metal compounds. (Eg, US Pat. No. 3,700,637, DE-A-25 39 132, EP-A-0 134 023, DE-OS-35 41 689, DE-OS). -35 40 918, EP-A-0 298 386, DE-OS-35 29 252, DE-OS-34 33 392, US Pat. No. 4,464,515, and US Pat. No. 4,503,196. See the specification).

  Suitable catalysts and solvents for hydrogenation in the homogeneous phase are described below and are also known from DE-A-25 39 132 and EP-A-0 471 250.

For example, selective hydrogenation can be carried out in the presence of a rhodium or ruthenium containing catalyst. For example, it is possible to use a catalyst of the following general formula:
(R ¹ _m B) _l MX _n
[Wherein M is ruthenium or rhodium, and the groups R ¹ may be the same or different, but are each a C ₁ -C ₈ -alkyl group, a C ₄ -C ₈ cycloalkyl group, a C _6- A C ₁₅ -aryl group or a C ₇ -C ₁₅ -aralkyl group, B is a phosphorus, arsenic, sulfur or sulfoxide group S═O and X is hydrogen or an anion, preferably halogen, particularly preferably chlorine or Bromine, l is 2, 3 or 4, m is 2 or 3, and n is 1, 2 or 3, preferably 1 or 3.] Suitable catalysts are tris (triphenylphosphine) Rhodium (I) chloride, tris (triphenylphosphine) rhodium (III) chloride, and tris (dimethylsulfoxide) rhodium (III) chloride; Is a tetrakis (triphenylphosphine) rhodium hydride of the formula (C ₆ H ₅ ) ₃ P) ₄ RhH and a corresponding compound in which all or part of the triphenylphosphine is substituted with tricyclohexylphosphine. A small amount of catalyst may be used. The amount is in the range from 0.01 to 1% by weight, preferably in the range from 0.03 to 0.5% by weight, particularly preferably in the range from 0.1 to 0.3% by weight, based on the weight of the polymer. Is preferable.

Usually, it is useful to use the catalyst with a cocatalyst, but the cocatalyst is a ligand of the formula R ¹ _m B, where R ¹ , m and B are described above for the catalyst. It has a meaning. m is preferably 3, B is preferably phosphorus, and the radicals R ¹ may be the same or different. 3 alkyl groups, 3 cycloalkyl groups, 3 aryl groups, 3 aralkyl groups, 2 aryls and 1 alkyl groups, 2 aryls and 1 cycloalkyl groups, 2 Having two alkyl and one aryl group, two alkyl and one cycloalkyl group, two cycloalkyl and one aryl group, or two cycloalkyl and one monoaryl group. Preferred cocatalysts are preferred.

  Examples of cocatalysts can be found, for example, in US Pat. No. 4,631,315. A preferred cocatalyst is triphenylphosphine. The cocatalyst is preferably used in an amount ranging from 0.3 to 5% by weight, preferably from 0.5 to 4% by weight, based on the weight of the nitrile rubber to be hydrogenated. Furthermore, the weight ratio of rhodium-containing catalyst to cocatalyst is in the range of 1: 3 to 1:55, particularly preferably in the range of 1: 5 to 1:45. Based on 100 parts by weight of the nitrile rubber to be hydrogenated, 0.1 to 33 parts by weight of cocatalyst, preferably 0.5 to 20 parts by weight, particularly preferably 1 to 5 parts by weight, in particular 2 parts by weight. It is appropriate to use a cocatalyst of greater than 5 but less than 5 parts by weight.

  Practical procedures for carrying out this hydrogenation are well known to those skilled in the art from US Pat. No. 6,683,136. Hydrogenation is usually carried out by exposing the nitrile rubber to be hydrogenated to hydrogen in a solvent such as toluene or monochlorobenzene at a temperature in the range of 100-150 ° C. and a pressure of 50-150 bar for 2-10 hours.

  For the purposes of the present invention, hydrogenation causes at least 50%, preferably 70-100%, particularly preferably 80-100%, of the double bonds present in the starting nitrile rubber to react. Further, the residual double bond content in HNBR is particularly preferably 0 to 8%.

  When heterogeneous catalysts are used, they are usually supported catalysts based on palladium, for example supported on carbon, silica, calcium carbonate or barium sulfate.

When hydrogenation is complete, a hydrogenated nitrile rubber is obtained having a Mooney viscosity (ML1 + 4, 100 ° C.) in the range of 10-50, preferably 10-30, as measured according to ASTM standard D1646. This, 2,000-400 000 g / mol, preferably in the range equivalent to 20 000-200 000 g / mol in the range of the weight-average molecular weight _{M w.} Further, the hydrogenated nitrile rubber thus obtained has a polydispersity PDI = M _w / M _{n in} the range of 1 to 5, preferably 1.5 to 3, where M _w is the weight average molecular weight. , M _n is the number average molecular weight).

If the catalyst of the present invention is used, very good results can be obtained in various forms of metathesis. When they are used for the decomposition of nitrile rubbers, it is possible to obtain decomposed nitrile rubbers with significantly reduced molecular weights M _w and M _n and good polydispersity.
[Example]

The prior art catalysts used in the following examples are:
"Grubbs (III) catalyst":

グラブスＩＩＩ触媒は、Ａｎｇｅｗ．Ｃｈｅｍ．Ｉｎｔ．Ｅｄ．、２００２、４１（２１）、４０３５の記載に従って調製した。

Grubbs III catalyst is available from Angew. Chem. Int. Ed. , 2002, 41 (21), 4035.

“Grubbs II Catalyst”:

このグラブスＩＩ触媒は、マテリア・インコーポレーテッド（Ｍａｔｅｒｉａ Ｉｎｃ．）（カリフォルニア州パサデナ（Ｐａｓａｄｅｎａ／Ｃａｌｉｆｏｒｎｉａ））から入手した。

The Grubbs II catalyst was obtained from Materia Inc. (Pasadena / California).

I. 1. Preparation of the catalyst of the invention 1.1 Dichloro (fluorenylidene) bis (triphenylphosphine) ruthenium (1)
1.1.1 Fluorenone-tosylhydrazone (A)
(D.A. Van Galen, J.H. Barnes, MD Hawley, J. Org. Chem.,). (Method based on the method of 1986, 51, 2544)

５．４１ｇの９−フルオレノン（３０ミリモル）、５．５９ｇのトルエン−４−スルホニルヒドラジド（９５％純度；３０ミリモル）および３０ｍＬのエタノールの混合物を、環流下で３０分間加熱した。これによって透明で黄色の溶液が得られたが、冷却して室温にすると、淡黄色の結晶がそれから沈殿してきた。その結晶を濾過し、２×３ｍＬのエタノールを用いて洗浄し、風乾させた。収量は９．５１ｇ（９１％）である。

A mixture of 5.41 g 9-fluorenone (30 mmol), 5.59 g toluene-4-sulfonylhydrazide (95% purity; 30 mmol) and 30 mL ethanol was heated at reflux for 30 minutes. This gave a clear yellow solution, but upon cooling to room temperature, pale yellow crystals precipitated from it. The crystals were filtered, washed with 2 × 3 mL ethanol and air dried. Yield is 9.51 g (91%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.37 (roads, 1H), 7.97 (d, J = 8.1 Hz, 2H), 7.87 (d, J = 7.7 Hz, 1H) 7.72 (d, J = 7.5 Hz, 1H), 7.65 (d, J = 7.5 Hz, 1H), 7.54 (d, J = 7.5 Hz, 1H), 7.45 ( t, J = 7.5 Hz, 1H), 7.39-7.30 (m, 4H), 7.26 (t, J = 7.5 Hz, 1H), 2.41 (s, 3H).

1.1.2 9-diazofluorene (B)
(Method based on the method of A. Jonczyk, J. Wlostowska, Synth. Commun., 1978, 8, 569)

２．０９ｇのフルオレノントシルヒドラゾン（１）（６ミリモル）、１５ｍＬのジオキサン、および２ｍＬの５０％強度のＮａＯＨ水溶液の混合物を、８５℃で１時間激しく撹拌した。この間に、元々は２相のオレンジ色の反応混合物が変色して赤色になった。ほんの１０分後には、ＴｓＮａが白色の沈殿物として沈殿しはじめた。その反応混合物を冷却して室温とし、１０ｍＬの水を混ぜ込んだ。その有機相を分離し、２×６ｍＬのペンタンを用いて残りの水相を抽出した。有機相を合わせ、２×４ｍＬの水で振盪させた。さらに乾燥させることなく、減圧下で溶媒を除去した。

A mixture of 2.09 g fluorenone tosylhydrazone (1) (6 mmol), 15 mL dioxane, and 2 mL 50% strength aqueous NaOH was stirred vigorously at 85 ° C. for 1 hour. During this time, the originally two-phase orange reaction mixture changed color to red. After only 10 minutes, TsNa began to precipitate as a white precipitate. The reaction mixture was cooled to room temperature and 10 mL of water was mixed in. The organic phase was separated and the remaining aqueous phase was extracted with 2 × 6 mL pentane. The organic phases were combined and shaken with 2 × 4 mL of water. The solvent was removed under reduced pressure without further drying.

  As a result, 9-diazofluorene (2) was obtained as an orange powder, and the yield was 1.08 g (94%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.96 (dm, J = 7.4 Hz, 2H), 7.52 (dm, J = 7.5 Hz, 2H), 7.40 (dt, J = 7 .4 and 1.3 Hz, 2H), 7.33 (dt, J = 7.4 and 1.3 Hz, 2H).

1.1.3 Preparation of dichloro (fluorenylidene) bis (triphenylphosphine) ruthenium (K1) (such as dichloro (fluorenylidene) bis (triphenylphosphine) ruthenium (K1) and fluorenylidenetriphenylphosphadine (P1) Molar mixture (as “K1 + P1”))

１．９１８ｇのＲｕＣｌ_２（ＰＰｈ_３）_３（２．０ミリモル）および１０ｍＬの乾燥ＣＨ_２Ｃｌ_２を、窒素雰囲気とマグネチックスターラーバーを備えたシュレンク容器の中に入れた。形成された溶液を加熱して４０℃とし、１０ｍＬの無水のＣＨ_２Ｃｌ_２中０．７６９ｇの９−ジアゾフルオレン（４．０ミリモル）の第二の溶液を、３０分間かけて滴下により添加した。次いでその混合物を、４０℃でさらに８０分間撹拌した。次いで高真空下で溶媒を除去した。そうして得られた反応生成物には、ルテニウムカルベンおよびホスファジンに加えて、^１Ｈ ＮＭＲ分光光度法^＊によって測定すると、約２．５モル％の未反応のＲｕＣｌ_２（ＰＰｈ_３）_３が含まれていた。この粗製物を精製するために、５×１２ｍＬのベンゼン／ヘキサン混合物（１：２）を用いてそれを完全に抽出した。

1.918 g of RuCl ₂ (PPh ₃ ) ₃ (2.0 mmol) and 10 mL of dry CH ₂ Cl ₂ were placed in a Schlenk vessel equipped with a nitrogen atmosphere and a magnetic stirrer bar. The solution formed was heated to 40 ° C. and a _second solution of 0.769 g 9-diazofluorene (4.0 mmol) in 10 mL anhydrous CH ₂ Cl ₂ was added dropwise over 30 minutes. . The mixture was then stirred at 40 ° C. for an additional 80 minutes. The solvent was then removed under high vacuum. The reaction product thus obtained contains about 2.5 mol% unreacted RuCl ₂ (PPh ₃ ) _{3 as} determined by ¹ H NMR spectrophotometry ^* in addition to ruthenium carbene and phosphadine. It was. To purify the crude, it was extracted completely with 5 × 12 mL benzene / hexane mixture (1: 2).

  Thereby, 2.57 g (97% yield) of red rust-colored powder was obtained.

^{From the 1} H NMR spectrum, this powder contained equimolar amounts of dichloro (fluorenylidene) bis (triphenylphosphine) ruthenium (K1) and fluorenylidenetriphenylphosphazine (P1). Corresponds to a carbene content of 65%. RuCl ₂ (PPh ₃ ) ₃ remained as an impurity at a concentration of about 0.8 mol%.

1.1.4 Dichloro (fluorenylidene) bis (triphenylphosphine) ruthenium (K1)
A column using silica gel (20 g) at −20 ° C. in a nitrogen atmosphere of the above-mentioned mixture (K1 + P1) (1.40 g) of dichloro (fluorenylidene) bis (triphenylphosphine) ruthenium and fluorenylidenetriphenylphosphadine. Separated by chromatography. Both the column and eluent (toluene / THF, 15: 1) were cooled to -20 ° C. About 100 mL of dark brown eluate was obtained, and then the solvent was removed to give 0.33 g of crude reaction product. Triphenylphosphine and a trace amount of RuCl ₂ (PPh ₃ ) ₃ remained as impurities in the fraction of the crude reaction product. Extraction with a benzene / hexane mixture (1: 2) gave the pure product K1.

¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ 7.45 (m, 14H), 7.41 (t, J = 7.5 Hz, 6H), 7.37 (d, J = 7.7 Hz, 2H) ), 7.30 (d, J = 7.3 Hz, 2H), 7.25 (t, J = 7.7 Hz, 12H), 6.40 (dt, J = 7.6 and 1.1 Hz, 2H) .

³¹ P NMR (202 MHz, CD ₂ Cl ₂ ): δ 32.2 (s).

_{^{13 C NMR (125MHz, CD 2}} Cl 2): δ 303.2 (t, C = Ru, J C-P = 12.3Hz), 147.8 (C), 139.0 (C), 135.4 _{(t, CH, J C-} P = 5.4Hz), 131.6 (d, CH, J C-P = 7.2Hz), 130.8 (t, C, J C-P = 21.5Hz) _{, 130.5 (CH), 129.3 (} CH), 128.2 (t, CH, J C-P = 4.8Hz), 117.8 (CH).

Analysis Calculated _{(C 49 H 38 Cl 2 P} 2 Ru): C: 68.37, H: 4.45. Found: C: 68.58, H: 4.53.

  Crystals of compound 1 suitable for X-ray structural analysis were obtained by gradually evaporating the benzene solution. FIG. 1 shows the structure of this compound. The selected bond distances (Å) are as follows: Ru—C1 1.862 (3), Ru—Cl1 2.3505 (8), Ru—Cl2 2.3487 (8), Ru—P1. 4070 (8), Ru-P2 2.4066 (9), C1-C2 1.479 (4), C1-C13 1.501 (4). Selected bond angles (degrees): C1-Ru-Cl1 99.49 (9), C1-Ru-Cl2 99.28 (9), Cl2-Ru-Cl1 161.23 (3), C1-Ru-P1 100.53 (8), C1-Ru-P2 99.03 (8), C1-Ru-P2 99.03 (8), C11-Ru-P1 84.98 (3), C11-Ru-P2 92. 42 (3), Cl2-Ru-P1 91.62 (3), Cl2-Ru-P2 84.62 (3), P1-Ru-P2 160.43 (3), C2-C1-Ru 128.8 ( 2), C13-C1-Ru 127.8 (2), C2-C1-C13 103.3 (2).

1.1.5 Fluorenylidene triphenylphosphazine (P1)
The phosphazine remaining on the column in the chromatography described above (1.1.4) can be eluted using the more polar eluent mixture toluene / THF (5: 1) means, Similarly obtained as a light brown fraction. After evaporating the eluate, the material is obtained in the form of yellow crystals from a methylene chloride / hexane mixture. The structure was determined by X-ray crystal structure analysis.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.21 (d, J = 7.7 Hz, 2H), 7.81 (dd, J = 12.5 and 7.8 Hz, 6H), 7.67 (dt , J = 7.2 and 1.2 Hz, 3H), 7.54 (dt, J = 7.8 and 3.0 Hz, 6H), 7.03 (t, J = 7.3 Hz, 2H), 6. 92 (t, J = 7.5 Hz, 2H), 6.38 (d, J = 8.0 Hz, 2H).

³¹ P NMR (121 MHz, CDCl ₃ ): δ 6.9 (s).

_{^{13 C NMR (75MHz, CDCl 3}} ): δ 141.6 (d, C, J C-P = 14.9Hz), 134.2 (d, CH, J C-P = 10.2Hz), 132.7 _{(d, CH, J C-} P = 2.8Hz), 130.8 (d, C, J C-P = 14.1Hz), 129.1 (d, CH, J C-P = 12.2Hz) _{, 125.7 (d, C, J} C-P = 88.5Hz), 122.8 (CH), 119.4 (d, CH, J C-P = 1.5Hz), 116.4 (CH) 115.9 (CH).

1.2 Dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (triphenylphosphine) ruthenium (K2)
(As an equimolar mixture of dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (triphenylphosphine) ruthenium (K2) and fluorenylidenetriphenylphosphazine (P1) ("K2 + P1"))

  In a Schlenk vessel, 0.729 g of 1,3-dimesitylimimidazolinium tetrafluoroborate (1.85 mmol) and 8 mL of dry tetrahydrofuran were mixed by means of a magnetic stir bar under a nitrogen atmosphere. . To the resulting suspension, 89 mg of sodium hydride (60% dispersion in mineral oil; 2.22 mmol) was slowly added. The formed white suspension was stirred for 2 hours and then filtered. The filtrate was evaporated to dryness and the resulting waxy solid was redissolved in 20 mL of dry diethyl ether.

  This ether solution of 1,3-dimesityldihydroimidazolylidene was added to a total of 2.44 g of dichloro (fluorenylidene) bis (triphenylphosphine) ruthenium and fluorenylidenetriphenylphosphadine in 20 mL of dry diethyl ether. To a suspension of an equimolar mixture ("K1 + P1") (65% purity; 1.84 mmol) under nitrogen. The reaction solution was stirred at room temperature for 2 hours and then filtered. Thorough extraction of the crude reaction product with 5 × 20 mL portions of diethyl ether resulted in trace amounts of dichloro (fluorenylidene) bis (1,3-dimesityldihydroimidazolylidene) ruthenium and unreacted dichloro (fluorenylidene). ) Bis (triphenylphosphine) ruthenium was removed.

  1.91 g (75% yield) of red rust powder remained.

According to the ¹ H NMR spectrum ^* , this material contains equivalent (mol / mol) dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (triphenylphosphine) ruthenium and fluorenylidenetriphenyl. Phosphazine (“K2 + P1”) is included, which corresponds to a K2 content of 65%. The residual amount of dichloro (fluorenylidene) bis (triphenylphosphine) ruthenium (K1) is about 1%, and the by-product 1,3-dimesityrylimidazolinium chloride is also about 1%.

1.2.2 Dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (triphenylphosphine) ruthenium (K2)
2.09 g equimolar mixture of dichloro (fluorenylidene) bis (triphenylphosphine) ruthenium (K1) and fluorenylidenetriphenylphosphazine (P1) (65% purity; 1.5 mmol) and 16 mL dry CH the ₂ Cl _2, and then introduced into a Schlenk vessel under nitrogen atmosphere. The solution was carefully covered with 50 mL of dry hexane and left to crystallize for 2 days. An additional 1.0 g of a brown powder was obtained by filtering the tan precipitate and evaporating the solvent from the filtrate. ^{From the 1} H NMR spectrum, it was found that the molar ratio of the components was K2: P1 = 3.4. Thorough washing with 5 × 30 mL of diethyl ether left 0.57 g of pure reaction product with a molar ratio of components K2: P1 = 27 (this corresponds to a K2 content of 98%).

¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ 7.81 (d, J = 7.7 Hz, 2H), 7.41 (t, J = 7.1 Hz, 2H), 7.23 (t, J = 7.3 Hz, 3H), 7.19 (s, 2H), 7.10 (d, J = 7.3 Hz, 2H), 6.99 (dt, J = 7.7 and 1.7 Hz, 6H) 6.92 (t, J = 8.5 Hz, 6H), 6.64 (t, J = 7.5 Hz, 2H), 5.86 (s, 2H), 4.02 (dd, J = 1.11. 8 and 8.9 Hz, 2H), 3.78 (dd, J = 11.8 and 8.9 Hz, 2H), 2.76 (s, 6H), 2.51 (s, 3H), 1.85 ( s, 3H), 1.84 (s, 6H).

³¹ P NMR (202 MHz, CD ₂ Cl ₂ ): δ 26.9 (s).

¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ 302.9 (d, C = Ru, J _C—P = 13.8 Hz), 212.1 (d, N—C—N, J _C—P = _{99.7Hz), 148.5 (d, C} , J C-P = 3.1Hz), 139.6 (C), 139.2 (C), 138.6 (C), 137.0 (C) , 136.9 (C), 136.5 ( C), 136.2 (C), 134.9 (d, CH, J C-P = 9.8Hz), 132.3 (C), 132.0 (C), 131.1 (CH) , 130.4 (CH), 130.2 (CH), 129.6 (d, CH, J C-P = 1.9Hz), 128.8 (CH), _{128.4 (CH), 116.5 (CH} ), 52.5 (d, CH 2, J C-P = 3.9Hz), 52.4 (d, CH 2, J C-P = 3 _{3Hz), 21.5 (CH 3)} , 20.6 (CH 3), 19.4 (CH 3).

Analysis Calculated _{(C 52 H 49 Cl 2 N} 2 PRu): C: 69.02, H: 5.46, N: 3.10. Found: C: 69.39, H: 5.61, N: 3.19.

  Crystals of compound 3 suitable for X-ray structural analysis were obtained from a benzene solution covered with hexane. FIG. 2 shows the structure of this compound. The selected bond distances (Å) are as follows: Ru-C1 1.861 (4), Ru-C14 2.088 (4), Ru-Cl1 2.3686 (10), Ru-Cl2. 3608 (10), Ru-P 2.4453 (11), C1-C2 1.502 (5), C1-C13 1.493 (5). Selected bond angles (degrees): C1-Ru-C14 97.37 (16), C1-Ru-Cl1 105.15 (12), C1-Ru-Cl2 100.50 (12), Cl2-Ru-Cl1 153.98 (4), C14-Ru-Cl1 85.13 (10), C14-Ru-Cl2 95.98 (10), C1-Ru-P 96.47 (12), C14-Ru-P 165. 99 (11), Cl1-Ru-P 89.16 (4), Cl2-Ru-P 83.62 (4), C2-C1-Ru 128.5 (3), C13-C1-Ru 127.2 ( 3), C2-C1-C13 104.3 (3), N1-C14-Ru 120.9 (3), N2-C14-Ru 132.0 (3).

1.3 Dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (pyridine) ruthenium (K3)

１３８ｍｇのジクロロ（フルオレニリデン）（１，３−ジメシチルジヒドロイミダゾリリデン）（トリフェニルホスフィン）ルテニウム（Ｋ２）（９８％純度：０．１５ミリモル）および０．３６ｍＬのピリジン（４．５ミリモル）を、窒素雰囲気下で、マグネチックスターラーバーを備えたシュレンク容器の中に導入した。その暗褐色の溶液を室温で３０分間撹拌し、次いで１０ｍＬの乾燥ヘキサンを添加した。暗黄色の沈殿物が生成するので、それから液体を注いだ。ヘキサン２ｍＬずつで３回その沈殿物を洗浄し、減圧下で乾燥させた。残存しているピリジンは、塩化メチレンと共に蒸留することにより除去した。

138 mg of dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (triphenylphosphine) ruthenium (K2) (98% purity: 0.15 mmol) and 0.36 mL of pyridine (4.5 mmol) Was introduced into a Schlenk vessel equipped with a magnetic stirrer bar under a nitrogen atmosphere. The dark brown solution was stirred at room temperature for 30 minutes and then 10 mL of dry hexane was added. A dark yellow precipitate formed and the liquid was then poured. The precipitate was washed 3 times with 2 mL of hexane and dried under reduced pressure. Residual pyridine was removed by distillation with methylene chloride.

  This gave 97 mg of catalyst K3, which corresponds to a yield of 90%.

¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ 8.08 (d, J = 7.6 Hz, 1H), 7.86 (d, J = 5.5 Hz, 1H), 7.49 (dt, J = 7.4 and 1.0 Hz, 2H), 7.44 (t, J = 7.6 Hz, 1H), 7.14 (s, 2H), 7.13 (d, J = 6.3 Hz, 2H) 6.94 (m, 4H), 6.08 (s, 2H), 4.08 (dd, J = 11.6 and 8.8 Hz, 2H), 3.81 (dd, J = 11.6 and 8.8 Hz, 2H), 2.83 (s, 6H), 2.35 (s, 3H), 1.93 (s, 3H), 1.89 (s, 6H).

¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ 301.3 (C = Ru), 210.5 (N—C—N), 153.0 (CH), 148.5 (C), 139.9 (C), 139.2 (C), 137.0 (C), 136.8 (CH), 136.7 (C), 135.6 (C), 135.5 (C), 130.6 (C) CH), 130.4 (CH), 129.7 (CH), 129.4 (CH), 128.5 (CH), 123.9 (CH), 117.1 (CH), 53.0 (CH _{2), 51.2 (CH 2)} , 21.2 (CH 3), 21.0 (CH 3), 20.7 (CH 3), 19.3 (CH 3).

Analysis Calculated _{(C 39 H 39 Cl 2 N} 3 Ru): C: 64.90, H: 5.45, N: 5.82. Found: C: 65.02, H: 5.52, N: 5.78.

  Crystals of compound 4 suitable for X-ray structural analysis were obtained from a benzene solution covered with hexane. FIG. 3 shows the structure of this compound.

  The selected bond distances (Å) are as follows: Ru-C1 1.860 (2), Ru-C14 2.068 (2), Ru-Cl1 2.3587 (6), Ru-Cl2. 3635 (6), Ru-N3 2.144 (2), C1-C2 1.487 (3), C1-C13 1.493 (3). Selected bond angles (degrees): C1-Ru-C14 99.41 (10), C1-Ru-Cl1 101.97 (7), C1-Ru-Cl2 97.78 (7), Cl2-Ru-Cl1 158.52 (3), C14-Ru-Cl1 85.58 (6), C14-Ru-Cl2 99.50 (6), C1-Ru-N3 92.70 (9), C14-Ru-N3 166. 75 (9), C11-Ru-N3 86.65 (6), Cl2-Ru-N3 84.06 (6), C2-C1-Ru 127.59 (17), C13-C1-Ru 126.94 ( 18), C2-C1-C13 104.8 (2), N1-C14-Ru 118.82 (18), N2-C14-Ru 131.59 (18).

1.4 Mixture of dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (pyridine) ruthenium (K3) and fluorenylidene triphenylphosphazine ("K3 + P1")

３３８ｍｇの、ジクロロ（フルオレニリデン）（１，３−ジメシチルジヒドロイミダゾリリデン）（トリフェニルホスフィン）ルテニウムとフルオレニリデントリフェニルホスファジンとの混合物（Ｋ２＋Ｐ１）（６５％純度；０．２４ミリモル）および０．９７ｍＬのピリジン（１２ミリモル）を、窒素雰囲気下で、マグネチックスターラーバーを備えたシュレンク容器の中に導入した。得られた褐色の懸濁液を室温で３０分間撹拌し、次いで２０ｍＬの乾燥ヘキサンを添加した。黄褐色の沈殿物から液体をデカントで除去し、次いで３×２ｍＬのヘキサンを用いてその沈殿物を洗浄した。減圧下で乾燥させると、２４２ｍｇの混合物Ｋ３＋Ｐ１（７３％収率）が得られた。^１Ｈ ＮＭＲスペクトル^＊から、モル比はＫ３：Ｐ１＝０．６９であり、これは、Ｋ３含量５２％に相当する。

338 mg of dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (triphenylphosphine) ruthenium and fluorenylidenetriphenylphosphazine (K2 + P1) (65% purity; 0.24 mmol) And 0.97 mL of pyridine (12 mmol) were introduced into a Schlenk vessel equipped with a magnetic stirrer bar under a nitrogen atmosphere. The resulting brown suspension was stirred at room temperature for 30 minutes and then 20 mL of dry hexane was added. The liquid was decanted off from the tan precipitate and then the precipitate was washed with 3 × 2 mL of hexane. Drying under reduced pressure gave 242 mg of mixture K3 + P1 (73% yield). ^{From the 1} H NMR spectrum ^* , the molar ratio is K3: P1 = 0.69, which corresponds to a K3 content of 52%.

1.5 Dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (3-bromopyridine) ruthenium (K4)

０．３７ｍＬの３−ブロモピリジン（３．７５ミリモル）を使用して、パラグラフ１．３に記載の手順を繰り返すと、ジクロロ（フルオレニリデン）（１，３−ジメシチルジヒドロイミダゾリリデン）（３−ブロモピリジン）ルテニウム（Ｋ４）がオレンジ〜褐色の反応生成物として、収量１１１ｍｇ（９２％）で得られた。

Repeating the procedure described in paragraph 1.3 using 0.37 mL of 3-bromopyridine (3.75 mmol) yields dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (3 -Bromopyridine) ruthenium (K4) was obtained as an orange-brown reaction product in a yield of 111 mg (92%).

¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ 8.27 (d, J = 2.1 Hz, 1H), 8.05 (d, J = 7.5 Hz, 2H), 7.59 (dm, J = 8.2 Hz, 1H), 7.52 (dd, J = 5.3 and 1.2 Hz, 1H), 7.50 (dt, J = 7.3 and 1.0 Hz, 6H), 7.14 ( s, 2H), 7.13 (d, J = 7.7 Hz, 2H), 6.95 (dt, J = 7.5 and 1.1 Hz, 2H), 6.76 (dd, J = 8.0). And 5.6 Hz, 1H), 6.08 (s, 2H), 4.09 (dd, J = 11.4 and 8.8 Hz, 2H), 3.82 (dd, J = 11.4 and 8. 8 Hz, 2H), 2.81 (s, 6H), 2.36 (s, 3H), 1.93 (s, 3H), 1.88 (s, 6H).

¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ 302.0 (C = Ru), 209.5 (N—C—N), 153.1 (CH), 152.0 (CH), 148.4 (C), 140.1 (C), 139.5 (CH), 139.3 (C), 139.1 (C), 137.0 (C), 136.7 (C), 135.5 ( C), 135.3 (C), 130.7 (CH), 130.4 (CH), 129.7 (CH), 129.4 (CH), 128.6 (CH), 124.8 (CH) ), 119.5 (C), 117.2 (CH), 53.1 (CH ₂ ), 51.1 (CH ₂ ), 21.3 (CH ₃ ), 21.0 (CH ₃ ), 20. _{6 (CH 3), 19.3 (} CH 3).

Analysis Calculated _{(C 39 H 38 BrCl 2 N} 3 Ru): C: 58.51, H: 4.78, N: 5.25. Found: C: 58.62, H: 4.82, N: 5.18.

  Catalyst K4 crystals suitable for X-ray structural analysis were obtained from a benzene solution covered with hexane. FIG. 4 shows the structure of this compound. The selected bond distances (Å) are as follows: Ru—C1 1.8570 (16), Ru—C14 2.0510 (16), Ru—Cl1 2.3681 (4), Ru—Cl2. 3678 (4), Ru-N3 2.1538 (14), C1-C2 1.496 (2), C1-C13 1.501 (2). Selected bond angles (degrees): C1-Ru-C14 99.68 (7), C1-Ru-Cl1 102.71 (5), C1-Ru-Cl2 96.91 (5), Cl2-Ru-Cl1 158.268 (16), C14-Ru-Cl1 85.63 (5), C14-Ru-Cl2 100.29 (5), C1-Ru-N3 93.85 (6), C14-Ru-N3 165. 25 (6), Cl1-Ru-N3 85.68 (4), Cl2-Ru-N3 83.76 (4), C2-C1-Ru 128.59 (12), C13-C1-Ru 126.73 ( 12), C2-C1-C13 104.05 (13), N1-C14-Ru 117.10 (12), N2-C14-Ru 134.76 (12).

1.6 Mixture of dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (3-bromopyridine) ruthenium and fluorenylidenetriphenylphosphazine (K4 + P1)

出発物質として０．７３ｍＬの３−ブロモピリジン（７．５ミリモル）を使用して、上述のパラグラフ１．４の手順を繰り返すと、３００ｍｇの、ジクロロ（フルオレニリデン）（１，３−ジメシチルジヒドロイミダゾリリデン）（３−ブロモピリジン）ルテニウムとフルオレニリデントリフェニルホスファジンとの混合物（Ｋ４＋Ｐ１）が、オレンジ〜褐色の反応生成物として得られた（８３％収率）。^１Ｈ ＮＭＲスペクトル^＊によれば、そのモル比はＫ４：Ｐ１＝０．７８であり、これはＫ４含量５７％に相当する。

Repeating the procedure in paragraph 1.4 above using 0.73 mL of 3-bromopyridine (7.5 mmol) as starting material yields 300 mg of dichloro (fluorenylidene) (1,3-dimesityldihydro A mixture of imidazolylidene) (3-bromopyridine) ruthenium and fluorenylidene triphenylphosphadine (K4 + P1) was obtained as an orange-brown reaction product (83% yield). According to the ¹ H NMR spectrum ^* , the molar ratio is K4: P1 = 0.78, which corresponds to a K4 content of 57%.

1.7 Dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (3-nitropyridine) ruthenium (K5)

１３８ｍｇのジクロロ（フルオレニリデン）（１，３−ジメシチルジヒドロイミダゾリリデン）（トリフェニルホスフィン）ルテニウムＫ２（９８％純度；０．１５ミリモル）、４６５ｍｇの３−ニトロピリジン（３．７５ミリモル）、および１．０ｍＬのトルエンを、窒素雰囲気下でマグネチックスターラーバーを備えたシュレンク容器の中に導入した。その褐色の懸濁液を室温で１時間撹拌してから、１０ｍＬの乾燥ヘキサンを添加した。そのオレンジ〜赤色の沈殿物から液体をデカントで除去し、３×２ｍＬのヘキサンを用いてその沈殿物を洗浄し、減圧下に乾燥させた。その沈殿物をまず０．２ｍＬのジクロロメタンの中に溶解させて、残存している３−ニトロピリジンを除去し、次いで２ｍＬのヘキサンを添加することによって、それを再び沈殿させた。

138 mg dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (triphenylphosphine) ruthenium K2 (98% purity; 0.15 mmol), 465 mg 3-nitropyridine (3.75 mmol), And 1.0 mL of toluene were introduced into a Schlenk vessel equipped with a magnetic stirrer bar under a nitrogen atmosphere. The brown suspension was stirred at room temperature for 1 hour and then 10 mL of dry hexane was added. The liquid was decanted from the orange-red precipitate and the precipitate was washed with 3 × 2 mL of hexane and dried under reduced pressure. The precipitate was first dissolved in 0.2 mL of dichloromethane to remove the remaining 3-nitropyridine and then it was precipitated again by adding 2 mL of hexane.

  This gave 103 mg of pure reaction product dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (3-nitropyridine) ruthenium (K5) (90% yield).

¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ 9.30 (s, 1H), 8.24 (d, J = 7.8 Hz, 1H), 8.00 (d, J = 7.6 Hz, 2H) ), 7.74 (d, J = 5.2 Hz, 1H), 7.50 (t, J = 7.3 Hz, 2H), 7.14 (s, 2H), 7.13 (d, J = 8) .3 Hz, 2 H), 7.04 (m, 1 H), 6.94 (t, J = 7.5 Hz, 2 H), 6.08 (s, 2 H), 4.11 (t, J = 10.1 Hz) , 2H), 3.84 (t, J = 10.1 Hz, 2H), 2.82 (s, 6H), 2.32 (s, 3H), 1.93 (s, 3H), 1.89 ( s, 6H).

¹³ C NMR (125 MHz, CD ₂ Cl ₂ ): δ 302.5 (C = Ru), 208.7 (N—C—N), 159.0 (CH), 148.4 (C), 147.9 (CH), 143.9 (C), 139.9 (C), 139.4 (C), 139.1 (C), 137.1 (C), 136.8 (C), 135.4 ( C), 135.2 (C), 131.6 (CH), 131.0 (CH), 130.4 (CH), 129.8 (CH), 129.4 (CH), 128.7 (CH) ), 124.2 (CH), 117.3 (CH), 53.0 (CH ₂ ), 51.2 (CH ₂ ), 21.2 (CH ₃ ), 21.0 (CH ₃ ), 20. _{6 (CH 3), 19.4 (} CH 3).

Analysis Calculated _{(C 39 H 38 Cl 2 N} 4 O 2 Ru): C: 61.09, H: 5.00, N: 7.31. Found: C: 60.74, H: 4.89, N: 7.27.

  Crystals of compound 6 suitable for X-ray structural analysis were obtained from a benzene solution covered with hexane. FIG. 5 shows the structure of this compound. The selected bond distances (Å) are as follows: Ru—C1 1.854 (6), Ru—C14 2.042 (6), Ru—Cl1 2.3597 (14), Ru—Cl2. 3705 (15), Ru-N3 2.139 (5), C1-C2 1.492 (8), C1-C13 1.491 (8).

  Selected bond angles (degrees): C1-Ru-C14 100.0 (3), C1-Ru-Cl1 96.15 (19), C1-Ru-Cl2 102.39 (19), Cl2-Ru-Cl1 159.14 (6), C14-Ru-Cl1 100.03 (16), C14-Ru-Cl2 86.19 (17), C1-Ru-N3 96.3 (2), C14-Ru-N3 163. 3 (2), Cl1-Ru-N3 81.95 (14), Cl2-Ru-N3 86.57 (14), C2-C1-Ru 127.2 (4), C13-C1-Ru 128.0 ( 5), C2-C1-C13 104.2 (5), N1-C14-Ru 116.2 (5), N2-C14-Ru 134.2 (4).

1.8 Mixture of dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (3-nitropyridine) ruthenium and fluorenylidenetriphenylphosphazine (K5 + P1)

１６９ｍｇの、ジクロロ（フルオレニリデン）（１，３−ジメシチルジヒドロイミダゾリリデン）（トリフェニルホスフィン）ルテニウムとフルオレニリデントリフェニルホスファジンとの混合物（「Ｋ２＋Ｐ１」）（６５％純度；０．１２ミリモル）、さらに３７２ｍｇの３−ニトロピリジン（３ミリモル）および０．８ｍＬのトルエンを、窒素雰囲気下でマグネチックスターラーバーを備えたシュレンク容器の中に導入した。その褐色の懸濁液を室温で１時間撹拌してから、８ｍＬの乾燥ヘキサンを添加した。その赤褐色の沈殿物から液体をデカントで除去し、３×１ｍＬのヘキサンを用いてその沈殿物を洗浄し、減圧下に乾燥させた。

169 mg of a mixture of dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (triphenylphosphine) ruthenium and fluorenylidenetriphenylphosphazine (“K2 + P1”) (65% purity; 0.12 Mmol), an additional 372 mg of 3-nitropyridine (3 mmol) and 0.8 mL of toluene were introduced into a Schlenk vessel equipped with a magnetic stir bar under a nitrogen atmosphere. The brown suspension was stirred at room temperature for 1 hour before 8 mL of dry hexane was added. The liquid was decanted from the reddish brown precipitate and the precipitate was washed with 3 × 1 mL of hexane and dried under reduced pressure.

This gave 139 mg of a mixture (K5 + P1) of dichloro (fluorenylidene) (1,3-dimesityldihydroimidazolylidene) (3-nitropyridine) ruthenium and fluorenylidenetriphenylphosphazine (82). %yield). According to the ¹ H NMR spectrum ^* , the molar ratio is K5: P1 = 0.73, which corresponds to a K5 content of 55%.

Explanation for all " ^* " marks:
^{* The} mixing ratio was determined in each case by the following ¹ H NMR signal (300 MHz, CD ₂ Cl ₂ ): RuCl ₂ (PPh ₃ ) ₃ (18H at 7.01 ppm), 1 (2H at 6.40 ppm) ), Phosphazine 2 (2H at 6.33 ppm), 3 (2H at 5.86 ppm), 4 (2H at 6.08 ppm), 5 (2H at 6.08 ppm), 6 (2H at 6.08 ppm). The content of 1,3-dimesityrylimidazolinium chloride was determined from the ratio of integral values for hydrogen atoms, comparing 4H at 4.4 ppm with 4H for carbene at 4.02 and 3.78 ppm. Unreacted dichloro (fluorenylidene) bis (triphenylphosphine) ruthenium could be determined by its ³¹ P NMR spectrum. The ratio of the 2P atoms at 31.3 ppm to the 1P integral of compound 3 at 26.0 ppm was employed.

Metathesis reaction using the catalyst according to the invention:
A “Ring-closing metathesis” under inert gas atmosphere
The suitability of the catalyst prepared in this invention for the ring closure metathesis of diethyl diallylmalonate and diallylmalononitrile is shown in the following examples.

For this purpose, in a glove box, an NMR tube with a Young valve was filled with the following: 24.0 mg in 0.6 mL CD ₂ Cl ₂ used as substrate. Of diethyl diallylmalonate or 14.6 mg of diallylmalononitrile (0.1 mmol in each case). 0.10 mL; the (1 micromolar 1 mol%) catalyst solution (0.50 mL _CD 2 Cl ₂ 5 micromolar catalyst) of was added at 23 to 25 ° C.. The reaction in which the cyclopentene derivative is formed is followed by ¹ H NMR spectrophotometry, starting material (2.61 ppm for diethyl diallyl malonate, 2.70 ppm for diallyl malononitrile) and reaction product (diethyl-3-cyclopentene- The amount was determined from the integrated value of the methylene proton signal of 2.98 ppm for 1,1-dicarboxylate and 3.22 ppm for 3-cyclopentene-1,1-dicarbonitrile. The overpressure that could occur due to the ethylene produced was carefully released.

  The results are shown in the following Tables A1 and A2.

A1 Ring-closing metathesis of diethyl diallylmalonate under inert gas atmosphere

A2 Ring-closing metathesis of diallylmalononitrile under inert gas atmosphere

A3 Ring-closing metathesis of diethyl diallylmalonate (DEDAM) under aerobic conditions From the following experiments, the catalyst of the present invention has a catalytic action on ring-closing metathesis of DEDAM under aerobic conditions. It can be seen that the addition of CaCl ₂ has a positive effect.

Ring closure metathesis of diethyl diallylmalonate was carried out using the catalyst according to the present invention with and without CaCl ₂ and without taking special measures to eliminate air and moisture. These experiments consisted of 0.151 mL (0.625 mmol) DEDAM, the catalysts and their amounts listed in the table below, 0.3 mL chlorobenzene, 0.2 mL CDCl ₃ , and optionally 1 mg CaCl _2. Was carried out.

In carrying out the experiments, the catalysts and amounts listed in the table were weighed into test tubes in a glove box and sealed using a septum in the glove box. Outside the glove box, non-deuterated chlorobenzene not saturated with 0.3 mL of nitrogen was added to the catalyst using a syringe to dissolve the catalyst. The catalyst solution was transferred to an NMR tube in air using a syringe. The test tube was then washed in air with 0.2 mL of deuterated chloroform (CDCl ₃ ) and transferred into the NMR tube using a syringe. In experiments where CaCl ₂ was added, an additional 1 mg of calcium chloride was introduced into the NMR tube. The reaction was started at room temperature by adding 0.151 mL (0.625 mmol) of DEDAM (ALDRICH). ¹ H NMR spectra were recorded at predetermined intervals to determine the conversion of the reaction.

B. Use of the catalyst according to the invention for the metathesis of nitrile rubber The decomposition reaction in the series of experiments 1 to 5 described below was carried out in accordance with the nitrile rubber Perbunan (registered by Lanxess Deutschland GmbH). Trademark: NT3435 was used. This nitrile rubber had the following characteristic values:
Acrylonitrile content: 34% by weight
Mooney viscosity (ML1 + 4, 100 ° C.): 35 Mooney unit residual moisture content: 1.8% by weight
_Mw : 186,000 g / mol _Mn : 60 000 g / mol PDI ( _Mw / _Mn ): 3.1

  Metathesis degradation was carried out in each case using 293 g of chlorobenzene (hereinafter abbreviated as “MCB”, manufactured by Acros Organics) without any further purification steps. In this, 40.0 g of NBR was dissolved over 10 hours at room temperature. To the NBR-containing solution, 800 mg (2 phr) of 1-hexane was added in each case and the mixture was homogenized by stirring for 10 minutes.

  The metathesis reaction was carried out at room temperature using the catalysts listed in the following table, but in each case 800 mg (2 phr) calcium chloride was added, once without calcium chloride. The catalysts were dissolved in 10 g MCB at room temperature under argon in each case. Immediately after preparing the catalyst solutions, they were added to the NBR solution in MCB. Approximately 5 mL samples of the reaction solution were taken after 30, 60, 90, 180, and 420 minutes, and immediately thereafter approximately 0.5 mL of ethyl vinyl ether was added to stop the reaction. 2 mL was taken from each of the solutions and diluted with 3 mL DMAc. To perform the GPC analysis, in each case, the solutions were added to a 0.2 μm syringe filter (Chromafil PTFE) 0.2 μm from Teflon; Macheley-Nagel -From Nagel)). A GPC analysis was then performed at 80 ° C., using a Polymer Laboratories PLgel precolumn and two 300 × 7.5 mm Resipore 3 μmPE columns. (Pump: Waters model 510).

  Calibration of the GPC column was performed using a linear poly (styrene) standard from Polymer Standards Services. As a detector, an RI detector (Waters 410) manufactured by Waters was used. The analysis was performed using DMAc (containing 0.075 mol / L LiBr) as an eluent at a flow rate of 1.0 mL / min. Evaluation of GPC curves was performed using software from Polymer Laboratories.

The following properties were determined by GPC analysis for both the original NBR rubber (before decomposition) and for the decomposed nitrile rubber:
_Mw / (kg / mol): Weight average molar mass _Mn / (kg / mol): Number average molar mass PDI: Width of molar mass distribution ( _Mw / _Mn )

1.00 Comparative experiment using Grubbs II catalyst

2.00 Experiment according to the invention using the mixture K2 + P1

3.00 Experiment according to the invention using the mixture K3 + P1

4.00 Experiment according to the invention using the mixture K4 + P1

5.00 Experiments according to the invention using the mixture K5 + P1

Claims (23)

Ruthenium- and osmium-carbene complexes containing the general structural element (I), where the carbon atom marked “ ^* ” is attached to the catalyst backbone through one or more double bonds A catalyst,

And R ^{1 to} R ⁸ may be the same or different and are each hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF ₃ , nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thio, respectively. Carbamate, dithiocarbamate, amino, amide, imino, silyl, sulfonate (—SO ₃ ^— ), —OSO ₃ ^— , —PO ₃ ^— or OPO ₃ ^— , or alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, Alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulfonyl, alkylsulfinyl, dialkylamino, alkylsilyl, or alkoxy Cisyl, wherein each of these groups is optionally substituted by one or more alkyl, halogen, alkoxy, aryl or heteroaryl groups, or alternatively, groups R ¹ -R Or two directly adjacent groups from ⁸ together with the ring carbon to which they are attached form a cyclic group, preferably an aromatic system, by bridge, or alternatively, R ⁸ may be bridged to other ligands of the ruthenium- or osmium-carbene complex catalyst, if appropriate,
m is 0 or 1, and A is oxygen, sulfur, C (R ⁹ R ¹⁰ ), N—R ¹¹ , —C (R ¹² ) = C (R ¹³ ) —, —C (R ¹² ) ^{(R 14) -C (R 13} ) (R 15) - it is a, wherein ^R 9 ^{to R 15} may be the same or different and each, one meaning of radicals ^R 1 to R ⁸ Having a catalyst.   The structural element of the general formula (I) is bonded to the central metal of the complex catalyst via a double bond, via 2, 3 or 4 integrated double bonds, or via a conjugated double bond. The catalyst according to claim 1. General formulas (IIa) and (IIb):

[Where:
M is ruthenium or osmium;
X ¹ and X ² may be the same or different, but are two ligands, preferably an anionic ligand,
L ¹ and L ² are the same or different ligands, preferably an uncharged electron donor, where L ² is instead bridged by the group R ⁸ You may,
n is 0, 1, 2 or 3, preferably 0, 1 or 2;
n ′ is 1 or 2, preferably 1, and R ^{1 to} R ⁸ , m, and A have the same meaning as in general formula (I) of claim 1]
The catalyst of Claim 1 represented by these. Including general structural elements (III) to (IX),

And here, the general structural elements (III) to (IX) are represented by the general formula (Xa) or (Xb) through one or more double bonds and through a carbon atom with “ ^* ”. ) Catalyst skeleton

Wherein X ¹ and X ² , L ¹ and L ² , n, n ′, and R ^{1 to} R ¹⁵ have the implications described in general formulas (IIa) and (IIb) of claim 3 The catalyst according to claim 1, wherein In the structural element of the general formula (I),
R ^{1 to} R ⁸ may be the same or different and are each hydrogen, halogen, hydroxyl, aldehyde, keto, thiol, CF ₃ , nitro, nitroso, cyano, thiocyano, isocyanato, carbodiimide, carbamate, thiocarbamate , dithiocarbamate, amino, amido, imino, silyl, sulphonate _{^{(-SO 3 -), - OSO}} 3 -, -PO 3 - or OPO ₃ ^-, or alkyl, preferably _C 1 _{-C 20} - alkyl, in particular _{C 1} -C ₆ - alkyl, cycloalkyl, preferably _C 3 _{-C 20} - cycloalkyl, in particular _C 3 -C ₈ - cycloalkyl, alkenyl, preferably _C 2 _{-C 20} - alkenyl, alkynyl, preferably _C 2 -C ₂₀ - alkynyl, aryl, preferably _C 6 _{-C 24} - aryl, in particular phenyl, carboxylate, preferably _C 1 _{-C 20} - carboxylate, alkoxy, preferably _C 1 _{-C 20} - alkoxy, alkenyloxy, preferably _C 2 _{-C 20} - alkenyloxy, alkynyloxy, preferably the _C 2 _{-C 20} - alkynyloxy, aryloxy, preferably _C 6 _{-C 24} - aryloxy, alkoxycarbonyl, preferably _C 2 _{-C 20} - alkoxycarbonyl, alkylamino, preferably _C 1 _{-C 30} - alkyl amino, alkylthio, preferably _C 1 _{-C 30} - alkylthio, arylthio, preferably _C 6 _{-C 24} - arylthio, alkylsulphonyl, preferably _C 1 _{-C 20} - alkylsulfonyl, alkylsulfinyl, preferably _{C 1} -C ₂₀ - alkylsulfinyl, dialkylamino, preferably di _(C 1 _{~C 20} - alkyl) amino, alkyl silyl, preferably _C 1 _{-C 20} - alkyl silyl or alkoxysilyl, preferably _C 1 _{-C 20,} - An alkoxysilyl group, wherein all of these groups may optionally be substituted by one or more alkyl, halogen, alkoxy-, aryl- or heteroaryl groups; Two directly adjacent groups from R ^{1 to} R ⁸ together with the ring carbon to which they are attached may form a cyclic group, preferably an aromatic system, by bridging. , or alternatively, optionally R ⁸ is, ruthenium - or osmium - bridge to other ligands carbene complex catalyst It may have been,
m is 0 or 1, and A is oxygen, sulfur, C (R ⁹ ) (R ¹⁰ ), N—R ¹¹ , —C (R ¹² ) ═C (R ¹³ ) —, or —C ( ^{R 12) (R 14) -C} (R 13) (R 15) - is a, wherein ^R 9 ^{to R 15} may be the same or different and those in each group ^R 1 to R ⁸ The catalyst according to claim 1, which can have the same preferred meaning as. X ¹ and X ² may be the same or different and are each hydrogen, halogen, pseudohalogen, linear or branched C ₁ -C ₃₀ -alkyl, C ₆ -C ₂₄ -aryl, C ₁ -C ₂₀ - _{alkoxy, C} 6 _{~C 24} - _{aryloxy, C} 3 _{~C 20} - alkyl _{diketonate, C} 6 _{~C 24} - aryl _{diketonate, C} 1 ~C ₂₀ - _{carboxylate, C} 1 ~ C ₂₀ - alkyl _{sulfonates, C} 6 _{~C 24} - aryl _{sulfonate, C} 1 _{~C 20} - _{alkylthiol, C} 6 _{~C 24} - aryl _{thiol, C} 1 _{~C 20} - alkylsulfonyl or _C 1 _{~C 20,} - alkyl The catalyst according to claim 3, which is a sulfinyl group. X ¹ and X ² may be the same or different and each is halogen, in particular fluorine, chlorine, bromine or iodine, benzoate, C ₁ -C ₅ -carboxylate, C ₁ -C ₅ -alkyl, _phenoxy, C 1 -C ₅ - _alkoxy, C 1 -C ₅ - alkyl _thiol, C 6 _{-C 24} - aryl _thiol, C 6 _{-C 24} - aryl or _C 1 -C ₅ - alkyl sulfonates, claim 3 The catalyst according to 1. X ¹ and X ² are the same and each is halogen, in particular chlorine, CF ₃ COO, CH ₃ COO, CFH ₂ COO, (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ) CO, ( _{CF 3) (CH 3) 2} CO, PhO ( phenoxy), MeO (methoxy), EtO (ethoxy), tosylate _{(p-CH 3 -C 6 H} 4 -SO 3), mesylate (2,4,6-trimethyl The catalyst according to claim 3, which is phenyl) or CF ₃ SO ₃ (trifluoromethanesulfonate). The two ligands L ¹ and L ² are independently of each other phosphine, sulfonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine. 4. The catalyst of claim 3, wherein the catalyst is a thioether or imidazolidine ("Im") ligand. One or both of the ligands L ¹ and L ² is a pyridine ligand, preferably pyridine, picoline (α-, β-, and γ-picoline), lutidine (2,3-, 2,4-, 2 , 5-, 2,6-, 3,4- and 3,5-lutidine), collidine (2,4,6-trimethylpyridine), trifluoromethylpyridine, phenylpyridine, 4- (dimethylamino) pyridine, Chloropyridine (2-, 3-, and 4-chloropyridine), bromopyridine (2-, 3-, and 4-bromopyridine), nitropyridine (2-, 3-, and 4-nitropyridine), quinoline, The catalyst according to claim 9, which is pyrimidine, pyrrole, imidazole, and phenylimidazole. One or both of the ligands L ¹ and L ² can be represented by the general formula (XIa) or (XIb):

[Where:
^{R 16, R 17, R 18} , R 19 may be the same or different and hydrogen, a linear or branched _C 1 _{-C 30} - _alkyl, C 3 _{-C 20} - cycloalkyl alkyl, C ₂ -C ₂₀ - _{alkenyl, C} 2 ~C ₂₀ - _{alkynyl, C} 6 _{~C 24} - _{aryl, C} 1 _{~C 20} - _{carboxylate, C} 1 _{~C 20} - _{alkoxy, C} 2 ~C ₂₀ - alkenyloxy, C ₂ -C ₂₀ - _{alkynyloxy, C} 6 _{~C 20} - _{aryloxy, C} 2 ~C ₂₀ - _{alkoxycarbonyl, C} 1 _{~C 20} - _{alkylthio, C} 6 _{~C 20} - _{arylthio, C} 1 _{~C 20} - alkylsulfonyl , _C 1 ~C ₂₀ - alkyl _{sulfonates, C} 6 _{~C 20} - arylsulfonate or _C 1 _{~C 20,} - at alkylsulfinyl I, optionally above group is preferably a halogen, especially chlorine or bromine, C 1 _-C 5 _- alkyl, C 1 _-C 5 _- alkoxy, and one or more selected from the group consisting of phenyl It may be monosubstituted or polysubstituted by a substituent which may be further substituted by a group.]
The catalyst according to claim 9, which is an imidazolidine group (Im) having the structure: One or both of the ligands L ¹ and L ² is one structure of the general formulas (XIIa) to (XIIf), where Mes is in each case 2,4,6-trimethylphenyl, 12. A catalyst according to claim 11 which is an imidazolidine group (Im) having or alternatively 2,6-diisopropylphenyl in all cases.

M is ruthenium,
X ¹ and X ² are both halogen,
In the general formula (IIa), n is 0, 1 or 2, or in the general formula (IIb), n ′ is 1.
L ¹ and L ² have the general or preferred meaning in the case of general formulas (IIa) and (IIb),
R ^{1 to} R ⁸ have the general or preferred meaning in the case of general formulas (IIa) and (IIb),
m is either 0 or 1,
And if m = 1,
A is oxygen, _{sulfur, C (C} 1 _{~C 10} - _{alkyl) 2, -C (C 1 ~C} 10 - _{alkyl) 2 -C (C 1 ~C 10} - _{alkyl) 2 -, - C (C} 1 -C ₁₀ - _{alkyl) = C (C 1 ~C 10} - alkyl) -, or _{-N (C} 1 _{~C 10} - alkyl),
4. A catalyst according to claim 3, of the general formula (IIa) or (IIb). M is ruthenium,
X ¹ and X ² are both chlorine,
In the general formula (IIa), n is 0, 1 or 2, or in the general formula (IIb), n ′ is 1.
L ¹ is an imidazolidine group having one of formulas (XIIa) to (XIIf);
L ² is a sulfonated phosphine, phosphate, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine group, an imidazolidine group having one of the formulas (XIIa) to (XIIf); Or phosphine ligands, in particular PPh ₃ , P (p-Tol) ₃ , P (o-Tol) ₃ , PPh (CH ₃ ) ₂ , P (CF ₃ ) ₃ , P (p-FC ₆ H ₄ ) _{3 , P (p-CF 3 C} 6 H 4) 3, P (C 6 H 4 -SO 3 Na) 3, P (CH 2 C 6 H 4 -SO 3 Na) 3, P ( _isopropyl) 3, P ( CHCH ₃ (CH ₂ CH ₃ )) ₃ , P (cyclopentyl) ₃ , P (cyclohexyl) ₃ , P (neopentyl) ₃ , or P (neophenyl) ₃ And
R ^{1 to} R ⁸ have the general or preferred meaning in the case of general formulas (IIa) and (IIb),
m is either 0 or 1,
And if m = 1,
A is oxygen, _{sulfur, C (C} 1 _{~C 10} - _{alkyl) 2, -C (C 1 ~C} 10 - _{alkyl) 2 -C (C 1 ~C 10} - _{alkyl) 2 -, - C (C} 1 -C ₁₀ - _{alkyl) = C (C 1 ~C 10} - alkyl) -, or _{-N (C} 1 _{~C 10} - alkyl),
4. A catalyst according to claim 3, of the general formula (IIa) or (IIb). Said group R ⁸ is bridged to another ligand of the complex catalyst to give a general formula (XIIIa) or (XIIIb):

[Where:
Y ¹ is oxygen, sulfur, N—R ²¹ group, or P—R ²¹ (R ²¹ is as defined below);
R ²⁰ and R ²¹ may be the same or different and are each alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio , Alkylsulfonyl, or alkylsulfinyl groups, all of which are optionally substituted by one or more alkyl, halogen, alkoxy, aryl, or heteroaryl groups,
When p is 0 or 1 and Y ² is p = 1, — (CH ₂ ) _r — (where r = 1, 2 or 3), —C (═O) —CH ₂ —, —C (═O) —, —N═CH—, —N (H) —C (═O) —, or alternatively, the entire structural unit “—Y ¹ (R ²⁰ )-(Y ² ) _p — ”is (—N (R ²⁰ ) ═CH—CH ₂ —), (—N (R ²⁰ , R ²¹ ) ═CH—CH ₂ —), and M, X ¹ , X ² , L ¹ , R ^{1 to} R ⁸ , A, m, and n have the same meaning as in the general formulas (IIa) and (IIb)]
The catalyst of Claim 3 which forms the structure of these. The following structural formula:

[Wherein Mes is in each case 2,4,6-trimethylphenyl and R ²⁰ and R ²¹ have the implications of claim 15]
A catalyst represented by The catalyst precursor compound is represented by the general formula (XVI):

[Wherein R ^{1 to} R ⁸ , m, and A have the meanings described in the general formula (I)]
A process for preparing a ruthenium- or osmium-carbene catalyst having a structural element of general formula (I) by reacting with a compound of
(I) the temperature is in the range of −20 ° C. to 100 ° C., preferably in the range of + 10 ° C. to + 80 ° C., particularly preferably in the range of +30 to + 50 ° C.
(Ii) The molar ratio of catalyst precursor compound to compound of general formula (XVI) is from 1: 0.5 to 1: 5, preferably from 1: 1.5 to 1: 2.5, particularly preferably 1. : 2
A method characterized by performing. A process for preparing a catalyst of the general formulas (IIa) and (IIb) according to claim 3, comprising the general formula (XVII):

[Where:
M, X ¹ , X ² , L ¹ and L ² have the same general and preferred meanings as in general formulas (IIa) and (IIb), and AbL is a “leaving ligand” A phosphine having the same meaning as L ¹ and L ² in general formulas (IIa) and (IIb), but preferably having one of the meanings mentioned in general formulas (IIa) and (IIb) Is a ligand]
The catalyst precursor compound of general formula (XVI):

[Wherein R ^{1 to} R ⁸ , m, and A have the meanings described in the general formula (I)]
And a temperature in the range of −20 ° C. to 100 ° C., preferably in the range of + 10 ° C. to + 80 ° C., particularly preferably in the range of +30 to + 50 ° C., and from 1: 0.5 to 1: 5, preferably 1 Reacting the catalyst precursor compound of the general formula (XVII) in a molar ratio to the compound of the general formula (XVI) of 1.5 to 1: 2.5, particularly preferably 1: 2.   Metathesis reactions, especially ring-closing metathesis (RCM), crossover metathesis (CM), ring-opening metathesis (ROM), ring-opening metathesis polymerization (ROMP), cyclic diene metathesis polymerization (ADMET), self-metathesis, reaction of alkenes with alkynes ( Use of a catalyst according to any one of claims 1 to 16 in enyne reactions), polymerization of alkynes, and olefination of carbonyls.   21. Use according to claim 19, wherein the catalyst according to any one of claims 1 to 16 is used to reduce the molecular weight of the nitrile rubber by contacting the nitrile rubber with a catalyst.   21. Use according to claim 20, wherein the amount of catalyst is 1 to 1000 ppm, preferably 2 to 500 ppm, in particular 5 to 250 ppm noble metal, based on the nitrile rubber used.   At least one conjugated diene, at least one α, β-unsaturated nitrile and, if appropriate, one or more further copolymerizable monomers, preferably fumaric acid, maleic acid, acrylic acid, methacrylic acid , Methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and Use according to claim 20 or 21, wherein a copolymer or terpolymer comprising repeating units of methoxyethyl (meth) acrylate is used as nitrile rubber.   Use according to any one of claims 20 to 22, wherein the hydrogenation is carried out after the decomposition of the nitrile rubber by metathesis to reduce the molecular weight.